[ CAS No. 201733-56-4 ] {[proInfo.proName]}

Name: 201733-56-4|5,5,5',5'-Tetramethyl-2,2'-bi(1,3,2-dioxaborinane)|98%
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Quality Control of [ 201733-56-4 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

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Product Details of [ 201733-56-4 ]

CAS No. :	201733-56-4	MDL No. :	MFCD02093062
Formula :	C₁₀H₂₀B₂O₄	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	MDNDJMCSXOXBFZ-UHFFFAOYSA-N
M.W :	225.89	Pubchem ID :	2734316
Synonyms :

Calculated chemistry of [ 201733-56-4 ]

Physicochemical Properties

Num. heavy atoms :	16
Num. arom. heavy atoms :	0
Fraction Csp3 :	1.0
Num. rotatable bonds :	1
Num. H-bond acceptors :	4.0
Num. H-bond donors :	0.0
Molar Refractivity :	63.4
TPSA :	36.92 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	Yes
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	Yes
Log Kp (skin permeation) :	-6.13 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	2.18
Log Po/w (WLOGP) :	1.19
Log Po/w (MLOGP) :	-0.21
Log Po/w (SILICOS-IT) :	-0.36
Consensus Log Po/w :	0.56

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	0.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-2.55
Solubility :	0.64 mg/ml ; 0.00283 mol/l
Class :	Soluble
Log S (Ali) :	-2.59
Solubility :	0.582 mg/ml ; 0.00258 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.12
Solubility :	1.72 mg/ml ; 0.00762 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	3.42

Safety of [ 201733-56-4 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 201733-56-4 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 201733-56-4 ]
Downstream synthetic route of [ 201733-56-4 ]

[ 201733-56-4 ] Synthesis Path-Upstream 1~8

1
[ 865-34-9 ]
[ 149817-62-9 ]
[ 201733-56-4 ]
[ 128143-86-2 ]
[ 1692-25-7 ]
[ 181866-50-2 ]
[ 381218-94-6 ]

Reference： [1] Journal of the Chemical Society. Perkin Transactions 2, 2002, # 10, p. 1669 - 1681

2
[ 1122-91-4 ]
[ 201733-56-4 ]
[ 128376-65-8 ]

Reference： [1] Tetrahedron Letters, 2012, vol. 53, # 46, p. 6230 - 6235,6

3
[ 2042-37-7 ]
[ 201733-56-4 ]
[ 214360-47-1 ]

Reference： [1] Tetrahedron Letters, 2005, vol. 46, # 10, p. 1671 - 1674

4
[ 126-30-7 ]
[ 201733-56-4 ]

Yield	Reaction Conditions	Operation in experiment
54.5%	With tetrakis(dimethylamido)diborane In toluene at 20 - 105℃; for 1.03333 h;	Tetrakis (dimethylamino) diboron (9.89 g, 52.65 mmol) was added to a solution of 2,2- dimethyl-1, 3-propanediol [neopentylglycol] (10.42 g, 100 mmol) in toluene (40 mL) at room temperature within two minutes. The mixture was heated to 105 C and an evolution of dimethylamine started to occur at 85 C. The mixture was heated for 60 minutes at 105 C then the toluene was removed to give a white solid: 11.39 g, 95.8percent. Recrystallisation from toluene gave bis (neopentylglycolato) boron (MF: CLOH20B204 ; FW: 225.89) 6.48 g, 54.5percent. mp 182.5-184. 5 C. 8 (CDCL3, 200 MHz) 0.94 (s, 12H); 3.58 (s, 6H) ppm. 13C 8 (CDCL3, 50 MHz) 22.3 (4x CH3) ; 31.9 (2x C), 71.7 (4x CH2) ppm. The mother liquor was kept for further recrystallization.

Reference： [1] Patent: WO2004/76467, 2004, A1, . Location in patent: Page 15

5
[ 13675-18-8 ]
[ 126-30-7 ]
[ 201733-56-4 ]

Reference： [1] Tetrahedron Letters, 2012, vol. 53, # 46, p. 6230 - 6235,6

6
[ 668987-38-0 ]
[ 201733-56-4 ]

Yield	Reaction Conditions	Operation in experiment
54%	for 8 h; Reflux; Inert atmosphere	Preparation of neopentyl glycol diboride: 4L BH3-THF (1 M) and 2.0 L of dichloromethane were added to the 20 L autoclave under a nitrogen atmosphere. After stirring well, the temperature was controlled to -10 ° C to 0 ° C, and 472 G of neopentyl glycol (4.0 mol) was dissolved in 0.5 L of a dichloromethane solution. Attention should be paid to control the bubble escape in the reactor during the dropping process. After the completion of the dropwise addition, the reaction was stirred for 3 to 5 hours. When the GC reaction was not changed, the methylene chloride was removed by distillation at atmospheric pressure. After adding 2 g of 2,6-di-tert-butyl-4-methylphenol, the reaction temperature was increased Pressure distillation to obtain 369 g of neopentylglycol borane as a colorless oily liquid, GC: 98.0percent, yield 81percent.(R = i-Pr), 70 g of cyclohexene and 550 mL of n-heptane were mixed and heated to the temperature of the system to maintain weak refluxing. 114 g of new catalyst was started to be added dropwise. Pentanediol borane (lmol), drop finished, continue to reflux stirring reaction 8 hours. After the reaction was complete, the reaction mixture was cooled down, filtered through Celite, evaporated to dryness, and 140 mL of n-heptane solvent was added to the mixture. The mixture was stirred at -10 ° C to -5 ° C for 1 to 2 hours and filtered to obtain 61.0 g of white crystalline bis Diol ester, GC: 99.4percent, yield 54percent.

Reference： [1] Patent: CN105524099, 2016, A, . Location in patent: Paragraph 0018

7
[ 1630-79-1 ]
[ 126-30-7 ]
[ 201733-56-4 ]

Reference： [1] Inorganic Chemistry, 1998, vol. 37, # 20, p. 5282 - 5288
[2] Tetrahedron Letters, 2012, vol. 53, # 46, p. 6230 - 6235,6

8
[ 122243-28-1 ]
[ 201733-56-4 ]
[ 1467061-57-9 ]

Yield	Reaction Conditions	Operation in experiment
74%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate In 1,4-dioxane at 110℃; for 1 h; Inert atmosphere; Microwave irradiation	A mixture of 2-(4-bromophenyl)-1,1,1-trifluoropropan-2-ol (300 mg, 1.12 mmol), 5,5,5',5'-tetramethyl-2,2'-bi-1,3,2-dioxaborinane (420 mg, 1.23 mmol), potassium acetate (500 mg, 5.10 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (90 mg, 0.11 mmol) was purged with N₂, suspended in degassed 1,4-dioxane (2.0 mL) and subjected to microwave irradiation at 110° C. for 60 minutes. The cooled reaction mixture was diluted with water (15 mL) and extracted with EtOAc (2*20 mL). The combined organic layers were washed with water and brine, dried over MgSO₄ and concentrated in vacuo. The resulting black oil was purified by flash chromatography (0-67percent EtOAc/heptane) to afford the title compound (249 mg, 74percent yield) as a pale yellow oil. GC/MS, M=302 at 3.58 min. ¹H NMR (400 MHz, CDCl₃) δ 7.81 (d, J=8.39 Hz, 2H), 7.54 (d, J=8.00 Hz, 2H), 3.76 (5, 4H), 1.77 (5, 3H), 1.01 (5, 6H).

Reference： [1] Patent: US2013/267493, 2013, A1, . Location in patent: Paragraph 1164

[ 201733-56-4 ] Synthesis Path-Downstream 1~88

1
[ 1885-38-7 ]
[ 201733-56-4 ]
3-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-3-phenyl-propionitrile [ No CAS ]

Reference： [1]Tetrahedron Letters,2002,vol. 43,p. 2323 - 2325

2
[ 865-34-9 ]
[ 149817-62-9 ]
[ 201733-56-4 ]
[ 128143-86-2 ]
[ 1692-25-7 ]
[ 181866-50-2 ]
[ 381218-94-6 ]

Reference： [1]Journal of the Chemical Society. Perkin Transactions 2 (2001),2002,p. 1669 - 1681

3
[ 149817-62-9 ]
[ 201733-56-4 ]
[ 1148-79-4 ]
[ 128143-86-2 ]
[ 381218-94-6 ]

Reference： [1]Journal of the Chemical Society. Perkin Transactions 2 (2001),2002,p. 1669 - 1681

4
[ 41085-43-2 ]
[ 201733-56-4 ]
[ 616227-09-9 ]

Reference： [1]Journal of Organometallic Chemistry,2003,vol. 680,p. 263 - 270
[2]Journal of Organometallic Chemistry,2003,vol. 680,p. 263 - 270

5
[ 1072-85-1 ]
[ 201733-56-4 ]
[ 346656-39-1 ]

Reference： [1]Tetrahedron Letters,2005,vol. 46,p. 1671 - 1674

6
[ 2042-37-7 ]
[ 201733-56-4 ]
[ 214360-47-1 ]

Reference： [1]Tetrahedron Letters,2005,vol. 46,p. 1671 - 1674

7
[ 5197-28-4 ]
[ 201733-56-4 ]
2-(2-methoxy-5-nitro-phenyl)-5,5-dimethyl-[1,3,2]dioxaborinane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃; for 0.166667h;Microwave irradiation;	Reference Example 18; 2-(5 , 5-Dimethyl[1,3,2]dioxaborinan-2-yl)-4-nitroanisole (Reference Compound No.18-1) A mixture of 2-Bromo-4-nitroanisole (100 mg, 0.431 mmol), bis(neopentylglycolate)diborane (151 mg, 0.668 mmol), potassium acetate (129 mg, 1.31 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]palladium(II )dichloride dichloromethane complex (1 : 1) (35.5 mg, 0.0435 mmol) was suspended in dimethylsulfoxide (3 mL), and the reaction mixture was stirred at 80C for 10 minutes under microwave. After cooling down, ethyl acetate (30 mL) and water (30 mL) were added to the reaction mixture and partitioned. The organic layer was washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure to give the titled reference compound (72.5 mg) as a yellow solid. (Yield 85%)
	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In dimethyl sulfoxide; at 50 - 80℃; for 3h;Inert atmosphere;	Dry DMSO (35 mL) was added to a mixture of PdCl2(dppf)-CH2Cl2 adduct (0.106 g, 0.129 mraol), potassium acetate (1.269 g, 12.93 mmol), bis(neopentyl glycolato)diboron (1.168 g, 5.17 mmoi) and <strong>[5197-28-4]2-bromo-4-nitroanisole</strong> (1 g, 4.31 mmol) and the resulting solution was degassed with N2. The reaction was heated at 50 C for 1 h then 80 C for 2 h. The reaction mixture was poured into ice- water and extracted with EtOAc (3 x) The combined extracts were washed with brine (2 x), dried (Na2S04) and concentrated in vacuo to give the crude product 2~(2-methoxy-5- nifrophenyl)-5,5-dime yl-1,3f2-dioxaborinane, which was used in the next step without further purification. NMR (500 MHz, CDC13): delta 8.56 (d, J = 3.0 Hz, 1 H); 8.27 (d, J - 9.3 Hz, 1 H); 6.92 (d, J - 9.1 Hz, 1 H); 3.95 (s, 3 H); 3.82 (s, 4 H); 1.07 (s, 6 H).

Reference： [1]Patent: EP1995242,2008,A1 .Location in patent: Page/Page column 47
[2]Tetrahedron Letters,2005,vol. 46,p. 1671 - 1674
[3]Patent: WO2012/58187,2012,A1 .Location in patent: Page/Page column 74

8
[ 78839-75-5 ]
[ 201733-56-4 ]
2-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-phenylamine [ No CAS ]

Reference： [1]Tetrahedron Letters,2005,vol. 46,p. 1671 - 1674

9
[ 149817-62-9 ]
[ 201733-56-4 ]
[ 381218-94-6 ]

Reference： [1]Inorganica Chimica Acta,2017,vol. 454,p. 27 - 39
[2]New Journal of Chemistry,2001,vol. 25,p. 1136 - 1147
[3]New Journal of Chemistry,2001,vol. 25,p. 1136 - 1147

10
[ 89972-76-9 ]
[ 201733-56-4 ]
[ 381218-92-4 ]

Reference： [1]Dalton Transactions,2011,vol. 40,p. 9189 - 9193
[2]Dalton Transactions,2011,vol. 40,p. 9189 - 9193
[3]New Journal of Chemistry,2001,vol. 25,p. 1136 - 1147
[4]New Journal of Chemistry,2001,vol. 25,p. 1136 - 1147
[5]Beilstein Journal of Organic Chemistry,2010,vol. 6

11
[ 915005-94-6 ]
[ 201733-56-4 ]
[ 915005-96-8 ]

Yield	Reaction Conditions	Operation in experiment
67%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 10h;	Example 15; 4-Cyano-lH-imidazole-2-carboxylic acid [4-(6-amino-pyridin-3-yl)-2-cyclohex-l-enyl-phenyl]- <n="49"/>amide, trifluoroacetic acid salt; a) 4-Cyano-l-(2-trimethylsilanyl-ethoxymethyl)-lH-imidazole-2-carboxylic acid [2- cyclohex- 1 -enyl-4-(5,5-dimethyl-[l ,3,2]dioxaborinan-2-yl)-phenyl]-amide; To a mixture of 4-cyano-l-(2-trimethylsilanyl-ethoxymethyl)-lH-imidazole-2-carboxylic acid (4-bromo-2-cyclohex-l-enyl-phenyl)-amide (as prepared in Example 11, step (f), 201 mg, 0.400 mmol), bis(neopentyl glycolato)diboron (108 mg, 0.480 mmol) and Pd(dppf)Cl2 (29.3 mg, 0.0400 mmol) in 4 mL of 1,4-dioxane was added KOAc (118 mg, 1.20 mmol). The resulting mixture was stirred at 80 C for 10 h under Ar. After cooling to RT, the mixture was treated with 50 mL of EtOAc, washed with H2O (3 x 10 mL) and brine (10 mL). The organic layer was dried (Na2SO4) and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (DCM) to afford 144 mg (67 %) of the title compound as a white solid: 1H-NMR (CDCl3; 400 MHz): delta 9.84 (s, IH), 8.35 (d, IH, J = 8.2 Hz), 7.76 (s, IH), 7.70 (dd, IH, J = 8.2, 1.4 Hz), 7.60 (d, IH, J = 1.4 Hz), 5.95 (s, 2H), 5.82 (m, IH), 3.76 (s, 4H), 3.65 (t, 2H, J = 8.1 Hz), 2.22- 2.35 (m, 4H), 1.68-1.92 (m, 4H), 1.01 (s, 6H), 0.96 (t, 2H, J = 8.1 Hz), 0.01 (s, 9H).

Reference： [1]Patent: WO2007/123516,2007,A1 .Location in patent: Page/Page column 46-47
[2]Bioorganic and Medicinal Chemistry Letters,2010,vol. 20,p. 3925 - 3929

12
[ 4766-33-0 ]
[ 201733-56-4 ]
[5-(5,5-dimethyl-[1,3,2]-dioxaborinan-2-yl)-naphthalen-1-yl]-amine [ No CAS ]

Reference： [1]Chemistry - A European Journal,2006,vol. 12,p. 1377 - 1384

13
[ 54962-75-3 ]
[ 201733-56-4 ]
[ 453560-89-9 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 4h;	N2 was bubbled through a solution of 3-bromo-5-trifluoromethyl-phenylamine (2.38 g), 5,5,5',5'-tetramethyl-[2,2']bi[[l,3,2]dioxaborinanyl] (2.24g, FrontierScientific) and KOAc (2.92 g), dppf (165 mg, Aldrich) inanhydrous dioxane (50 ml) for 2 min. PdCl2 (dppf) (243 mg,Aldrich) was added and the reaction was heated to 80°C for 4h. After cooling to RT, the mix was diluted with 50 mL ofEt20, filtered through Celite.(R)., and the filtrate wasconcentrated in vacua. The residue was dissolved in Et20(100 mL) , washed with sat. NaHC03 aqueous solution (50 mL)followed by brine (50 mL). The organic phase was dried overNa2SO4 and concentrated in vacua. The residue wasdissolved in 3:2 Et20/Hex (100 mL) , filtered through Celite.(R).and the filtrate was concentrated in vacua to afford a darkbrown semi-solid.
	With 1,1'-bis-(diphenylphosphino)ferrocene; potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 4.03333h;	N2 was bubbled through a solution of 3-bromo-5-trifluoromethyl-phenylamine (2.38 g), 5,5,5',5'-tetramethyl-[2,2']bi[[1,3,2]dioxaborinanyl](2.24 g, Frontier Scientific) and KOAc (2.92 g), dppf (165 mg, Aldrich) in anhydrous dioxane (50 ml) for 2 min. PdCl2 (dppf) (243 mg, Aldrich) was added and the reaction was heated to 80° C. for 4 h. After cooling to RT, the mix was diluted with 50 mL of Et2O, filtered through Celite.(R)., and the filtrate was concentrated in vacuo. The residue was dissolved in Et2O (100 mL), washed with sat. NaHCO3 aqueous solution (50 mL) followed by brine (50 mL). The organic phase was dried over Na2SO4 and concentrated in vacuo. The residue was dissolved in 3:2 Et2O/Hex (100 mL), filtered through Celite.(R). and the filtrate was concentrated in vacuo to afford a dark brown semi-solid.
	With potassium acetate;1,1'-bis-(diphenylphosphino)ferrocene; (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 4h;	Preparation [LIX-3- (5, 5-DIMETHYL- [1,] 3,2] dioxaborinan-2-yl) - 5-trifluoromethyl-phenylamine N2 was bubbled through a solution of 3-bromo-5- trifluoromethyl-phenylamine (2.38 g), 5,5, 5', 5'-tetramethyl- [[2,] [2APOS;] BI [ [1,] 3, [2] DIOXABORINANYL]] (2.24 g, Frontier Scientific) and KOAc (2.92 g), dppf (165 mg, Aldrich) in anhydrous dioxane (50 mL) for 2 min. [PDCL2] (dppf) (243 mg, Aldrich) was added and the reaction was heated to [80 °C] for 4 h. After cooling to RT, the mix was diluted with 50 mL of [ET20,] filtered through [CELTECOMMAT;, ] and the filtrate was concentrated in vacuo. The residue was dissolved in [ET20] (100 mL), washed with sat. [NAHC03] aqueous solution (50 mL) followed by brine (50 mL). The organic phase was dried over [NA2SO4] and concentrated in vacuo. The residue was dissolved in 3: 2 [ET2O/HEX] (100 mL), filtered through [CELITES] and the filtrate was concentrated in vacuo to afford a dark brown semi-solid.

Reference： [1]Patent: WO2006/12374,2006,A1 .Location in patent: Page/Page column 153-154
[2]Patent: US2003/225106,2003,A1 .Location in patent: Page 78
[3]Patent: WO2004/5279,2004,A2 .Location in patent: Page 113

14
[ 2077-19-2 ]
[ 201733-56-4 ]
[ 639482-03-4 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In DMF (N,N-dimethyl-formamide); at 60℃; for 18h;	A mixture [OF 2- (4-BROMOPHENYL) PROPAN-2-OL] (3.50g, 16. [3MMOL),] bis [(NEOPENTYLGLYCOLATO) DIBORON] (4.05g, 17. [93MMOL),] [KOAC] (2.40g, 24. [45MMOL)] and [1,1'-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (665mg, 0. [815MMOL)] in DMF (25mL) was heated at [60FOR] 18h. The DMF was removed in vacuo and the residue azeotroped with toluene (x 3). The residue was dissolved in [ET20,] filtered, and the filtrated concentrated in vacuo to give the title compound as a brown solid (3.08g). 8H [(CDCI3)] 7.70 (2H, d, J 9.8Hz), 7.41 (2H, d, J 9.8Hz), 3.69 (4H, s), 1.51 (6H, s), 0.95 (6H, [S).]

Reference： [1]Patent: WO2004/846,2003,A1 .Location in patent: Page 90

15
[ 686344-10-5 ]
[ 201733-56-4 ]
[ 849549-65-1 ]

Yield	Reaction Conditions	Operation in experiment
83%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; dimethyl sulfoxide; at 90℃; for 16.5h;	Step 3; A solution of the triflate from Step 2 (2.546 g, 7.6 mmol), bis (neopentyl glycolato) diboron (2.064 g, 9.1 mmol) and KOAC (1.495 g, 15.2 mmol) in dioxane (27 mL) and DMSO (3 mL) was deoxygenated by bubbling nitrogen through the solution for 20 minutes. [1,1'-Bis (DIPHENYLPHOSPHINO) ferrocene] palladium (II) chloride (0.622 g, 0.76 mmol) was added and deoxygenation was continued for a further 10 minutes. The reaction was heated at 90C for 16 hours, then allowed to cool and diluted with water (40 mL). The reaction was extracted with EtOAc (x3). The combined extracts were washed with water then brine, dried (MGS04), filtered and evaporated. The residue was purified by chromatography on silica, eluting with 20% ETOAC/HEXANE to give the product (1.881 g, 83%). (360MHZ IH, 6-CDC13) 1.04 (6H, s), 1.30 (2H, M), 1.83 (2H, M), 2.59 (2H, M), 2.85-3. 00 (4H, M), 3.78 (4H, s), 7.19 (1H, M), 7.62 (2H, M).
83%		A solution of the triflate from Step 2 (2.546 g, 7.6 mmol), bis(neopentyl glycolato)diboron (2.064 g, 9.1 mmol) and KOAc (1.495 g, 15.2 mmol) in dioxane (27 mL) and DMSO (3 mL) was deoxygenated by bubbling nitrogen through the solution for 20 minutes. [1,1'-Bis (diphenylphosphino)ferrocene] palladium (II) chloride (0.622 g, 0.76 mmol) was added and deoxygenation was continued for a further 10 minutes. The reaction was heated at 90 C. for 16 hours, then allowed to cool and diluted with water (40 mL). The reaction was extracted with EtOAc (x3). The combined extracts were washed with water then brine, dried (MgSO4), filtered and evaporated. The residue was purified by chromatography on silica, eluting with 20% EtOAc/hexane to give the product (1.881 g, 83%). (360 MHz 1H, delta-CDCl3) 1.04 (6H, s), 1.30 (2H, m), 1.83 (2H, m), 2.59 (2H, m), 2.85-3.00 (4H, m), 3.78 (4H, s), 7.19 (1H, m), 7.62 (2H, m).

Reference： [1]Patent: WO2005/30731,2005,A1 .Location in patent: Page/Page column 18
[2]Patent: US2005/143369,2005,A1 .Location in patent: Page/Page column 8-9

16
[ 800384-33-2 ]
[ 201733-56-4 ]
[ 800384-42-3 ]

Yield	Reaction Conditions	Operation in experiment
70%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 17.1667h;	A mixture of 4-BROMO-1-P-METHOXYPHENYLSULFONYL-2- (3, 4, 5-trimethoxyphenyl)-pyrrole (46 mg, 0.9 MMOL, Example 100b), bis (neopentylglycolato) diboron (37 mg, 1.8 equiv. ), potassium acetate (274 mg, 3.1 equiv. ) and PdCl2 (DPPF) ( [1, 1'-bis (diphenylphosphino)- ferrocene] PALLADIUM (II) DICHLOROMETHANE adduct, 74 mg, 0.1 equiv. ) is evacuated for 10 min and set under argon atmosphere, followed by addition of degassed dioxane (8 ml). The reaction mixture is heated for 17 h at 80C, cooled to room temperature and diluted with water and ethyl acetate. The organic layer is dried (MGS04), filtered and the solvents are evaporated. The residue is chromatographed with ethyl acetate/hexane to yield the title compound (0.3 g, 70%) as a white foam.'H-NMR (300 MHz, DMSO-D6) : 7.61 (d, J=1.7, 1H) ; 7.33 (d, J=9.0, 2H); 6.99 (d, J=9. 0,2H) ; 6.36 (s, 2H); 6.30 (d, J=1.7, 1H) ; 3.80 (s, MeO) ; 3.71 (s, MeO) ; 3.70 (s, 2CH2); 3.67 (s, 2MEO) ; 0.95 (s, 2CH3).

Reference： [1]Patent: WO2004/103968,2004,A1 .Location in patent: Page 70

17
[ 864773-02-4 ]
[ 201733-56-4 ]
[ 864775-20-2 ]

Yield	Reaction Conditions	Operation in experiment
78%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 3h;	A mixture of the compound of Example 70 (a) (960 mg, 2.00 mmol), 5,5, 5', 5'-tetramethyl-2, 2'-bi-1,3, 2-dioxaborinane (542 mg, 2. 4mol.), PddppfCI2CH2CI2 (100 mg, 5 mol%), KOAc (294 mg, 3. 0mmol.) and dioxane (20 mL) was heated at 80 C under N2 protection for 3hrs. Reaction mixture was concentrated and purified on Biotage column (20% to 50% EtOAc/CH2CI2 with 1% HOAc) to give the title compound as yellow solid 800mg. (yield 78%).

Reference： [1]Patent: WO2005/85227,2005,A1 .Location in patent: Page/Page column 139

18
[ 201733-56-4 ]
[ 52727-57-8 ]
[ 872460-04-3 ]

Yield	Reaction Conditions	Operation in experiment
75%	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In dimethyl sulfoxide; at 80℃; for 5h;	Example 54; 2-Amino-5-(2-11-[(4-aminomethyl-cyclohexanecarbonyl)-aminol-2-phenyl-ethyll- pyridin-4-yl)-benzoic acid methyl ester, tris-trifluroacetic acid salt; [00404] 54A. 2-Amino-5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-benzoic acid methyl ester: To a flame-dried, round-bottom flask equipped with a condenser was added 2-Amino-5-bromo-benzoic acid methyl ester (0.7 g, 3.0 mmol), Pd (dppf)Cl2No.CH2Cl2 complex (0.106 g, 0.130 mmol), KOAc (1.28 g, 13.0 mmol), and bis(neopentyl glycolato) diboron (1.08 g, 4.78 mmol). Next degassed DMSO (29 mL) was added and the reaction was stirred at 80 C. After 5 h, the reaction was cooled to rt, diluted with EtOAc (100 mL), washed with water, brine, dried over Na2S04, filtered and concentrated. Column chromatography on silica gel (gradient elution 0- 20% EtOAc/Hexane) gave 54A (0.858 g, 75%) as a white solid. ¹H NMR (400 MHz, CDC13) 8: 1.01 (s, 6 H), 3.74 (s, 4 H), 3.86 (s, 3 H), 5.91 (bs, H), 6.63 (d, J = 8.3 Hz, 1 H), 7.66-7.68 (m, 1 H), 8.33 (s, 1 H). MS 196.1 (M - C5H8 + H)+.

Reference： [1]Patent: WO2005/123680,2005,A1 .Location in patent: Page/Page column 102

19
[ 181180-42-7 ]
[ 201733-56-4 ]
[ 885693-10-7 ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 8h;	A mixture of trifluoromethanesulfonic acid 3,6-dihydro-2H-thiopyran-4-yl ester (as prepared in Example 35, step (a), 500 mg, 2.01 mmol), bis(neopentyl glycolato)diboron (478 mg, 2.11 mmol), Pd(dppf)Cl2 (147 mg, 0.20 mmol) and KOAc (592 mg, 6.03 mmol) in 8 mL of 1,4-dioxane was stirred at 80 C for 8 h under Ar, and then cooled to RT.Treated with 50 mL of EtOAc, the mixture was washed with H2O (2 x 10 mL), brine (10 mL) and dried (Na2SO4). Removal of the solvent under reduced pressure followed by flash chromatography of the residue on silica gel (0-5 % EtOAc/DCM) gave 351 mg (82 %) of the title compound as a colorless oil. 1H-NMR (CDCl3; 400 MHz): delta 6.62 (m, IH), 3.63 (s, 4H), 3.21 (m, 2H), 2.68 (t, 2H, J = 5.8 Hz), 2.37 (m, 2H), 0.96 (s, 6H). Mass spectrum (ESI, m/z): Calcd. for Ci0Hi7BO2S, 213.1 (M+H), found 213.1.
82%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 8h;	A mixture of trifluoromethanesulfonic acid 3,6-dihydro-2H-thiopyran-4-yl ester (as prepared in Example 35, step (a), 500 mg, 2.01 mmol), bis(neopentyl glycolato)diboron (478 mg, 2.11 mmol), Pd(dppf)Cl2 (147 mg, 0.20 mmol) and KOAc (592 mg, 6.03 mmol) in 8 mL of 1,4-dioxane was stirred at 80 C. for 8 h under Ar, and then cooled to RT. Treated with 50 mL of EtOAc, the mixture was washed with H2O (2×10 mL), brine (10 mL) and dried (Na2SO4). Removal of the solvent under reduced pressure followed by flash chromatography of the residue on silica gel (0-5% EtOAc/DCM) gave 351 mg (82%) of the title compound as a colorless oil. 1H-NMR (CDCl3; 400 MHz): delta 6.62 (m, 1H), 3.63 (s, 4H), 3.21 (m, 2H), 2.68 (t, 2H, J=5.8 Hz), 2.37 (m, 2H), 0.96 (s, 6H). Mass spectrum (ESI, m/z): Calcd. for C10H17BO2S, 213.1 (M+H), found 213.1.
82%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 8h;	a) 2-(3,6-Dihydro-2H-thiopyran-4-yl)-5,5-dimethyl-[1,3,2]dioxaborinane A mixture of trifluoromethanesulfonic acid 3,6-dihydro-2H-thiopyran-4-yl ester (as prepared in Example 35, step (a), 500 mg, 2.01 mmol), bis(neopentyl glycolato)diboron (478 mg, 2.11 mmol), Pd(dppf)Cl2 (147 mg, 0.20 mmol) and KOAc (592 mg, 6.03 mmol) in 8 mL of 1,4-dioxane was stirred at 80 C. for 8 h under Ar, and then cooled to RT. Treated with 50 mL of EtOAc, the mixture was washed with H2O (2*10 mL), brine (10 mL) and dried (Na2SO4). Removal of the solvent under reduced pressure followed by flash chromatography of the residue on silica gel (0-5% EtOAc/DCM) gave 351 mg (82%) of the title compound as a colorless oil. 1H-NMR (CDCl3; 400 MHz): delta 6.62 (m, 1H), 3.63 (s, 4H), 3.21 (m, 2H), 2.68 (t, 2H, J=5.8 Hz), 2.37 (m, 2H), 0.96 (s, 6H). Mass spectrum (ESI, m/z): Calcd. for C10H17BO2S, 213.1 (M+H). found 213.1.

82%

With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 80℃; for 8h;

of trifluoromcthancsulfonic acid 3,6-dihydro-2H-thiopyran-4-yl ester (as prepared in Example 35, step (a), 500 mg, 2.01 mmol), bis(neopentyl glycolato)diboron (478 mg, 2.11 mmol), Pd(dppf)Cl2 (147 mg, 0.20 mmol) and KOAc (592 mg, 6.03 mmol) in 8 mL of 1,4-dioxane was stirred at 80 C for 8 h under Ar, and then cooled to RT. Treated with 50 mL of EtOAc, the mixture was washed with H2O (2 x 10 mL), brine (10 mL) and dried (Na2SO4). Removal of the solvent under reduced pressure followed by flash chromatography of the residue on silica gel (0-5 % EtOAc/DCM) gave 351 mg (82 %) of the title compound as a colorless oil. 1H-NMR (CDCl3; 400 MHz): delta 6.62 (m, IH), 3.63 (s, 4H), 3.21 (m, 2H), 2.68 (t, 2H, J = 5.8 Hz)5 2.37 (m, 2H), 0.96 (s, 6H). Mass spectrum (ESI, m/z): Calcd. for C10H17BO2S, 213.1 (M+H), found 213.1.

Reference： [1]Patent: WO2006/47277,2006,A2 .Location in patent: Page/Page column 81-82
[2]Patent: US2006/281788,2006,A1 .Location in patent: Page/Page column 66
[3]Patent: US2008/51402,2008,A1 .Location in patent: Page/Page column 52
[4]Patent: WO2007/48088,2007,A2 .Location in patent: Page/Page column 99

20
3'-bromo-6,2',6'-frifluorobiphenyl-2-carbonitrile [ No CAS ]
[ 201733-56-4 ]
[ 624741-55-5 ]

Yield	Reaction Conditions	Operation in experiment
57%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; dimethyl sulfoxide; at 85℃; for 18h;	A mixture of 3'-bromo-6, 2', 6'-trifluorobiphenyl-2-carbonitrile (0.3745 g, 1.20 mmol), dried potassium acetate (0.2327 g, 2.37 mmol) and bis (neopentyl glycolato) diboron (0.3529 g, 1.56 mmol) in 1,4-dioxane (9.8 ml) and dimethylsulfoxide (0.2 ml) was degassed by bubbling nitrogen through the mixture for 1 h. Dichloro [1, 1'-bis (diphenylphosphino) - ferrocene] palladium (II) dichloromethane adduct (30.0 mg, 0.037 mmol) was added and the mixture was heated at 85C under nitrogen for 18 h. After allowing to cool, the mixture was diluted with diethyl ether (10 ml), filtered through glass fibre paper, and the solid was washed with diethyl ether. The combined filtrates were evaporated in vacuo and the residue was dissolved in diethyl ether (20 ml) and extracted with 1 N aqueous NaOH (2 x 20 ml). The combined aqueous extracts were then acidified to pH 5 with concentrated hydrochloric acid and extracted with diethyl ether (2 x 20 ml). The combined organic extracts were washed with saturated aqueous NaCl (10 ml), dried (MgSO4) and evaporated in uacuo to afford 0.2401 g (57%) of the title compound as a brown oil: IH NMR (360 MHz, CDC1s) 5 1.04 (6H, s), 3.79 (4H, s), 7.04 (1H, t, J 8. 8), 7.42 (1H, td, J 8. 8, 1. 1), 7.52 (1H, td, J8. 4,4. 9), 7.59 (1H, dd, J7. 7,1. 1), 7.88 (1H, dt, J8. 4, 7.0).

Reference： [1]Patent: WO2003/93272,2003,A1 .Location in patent: Page/Page column 39

21
[ 105942-08-3 ]
[ 201733-56-4 ]
[ 898803-13-9 ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In methanol; for 18h;Heating / reflux;	Example 80 6-Amino-N-{1-[3-(3-amino-benzo[d]isoxazol-6-yl)-phenyl]-2-phenyl-ethyl}-nicotinamide 80A. 4-(5,5-Dimethyl-[1,3,2]dioxaborinan-2-yl)-2-fluoro-benzonitrile: To 4-bromo-2-fluorobenzonitrile (15 g, 75.0 mmol) in MeOH (250 mL) were added bis(neopentylglycolato)diboron (18.6 g, 82.5 mmol), KOAc (11.0 g, 112.5 mmol), and Pd(dppf)Cl2.CH2Cl2. The reaction was heated at reflux for 18 h. The reaction was cooled, diluted with Et2O, filtered through Celite and the filtrate was concentrated. The residue was re-dissolved in Et2O, washed with water, brine and dried (MgSO4). After filtration and concentration 16.89 g (97%) of an orange solid was obtained and used without further purification. 1H NMR (400 MHz, CDCl3) delta: 7.65-7.58 (m, 3H), 3.78 (s, 4H), 1.02 (s, 6H).

Reference： [1]Patent: US2006/154915,2006,A1 .Location in patent: Page/Page column 35

22
[ 854044-45-4 ]
[ 201733-56-4 ]
[ 885704-74-5 ]

Yield	Reaction Conditions	Operation in experiment
70%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In methanol; at 60℃; for 5h;	b) l-[5-(5,5-Dimethyl-[l,3,2]dioxaborinan-2-yl)-2-nitro-phenyl]-4-methyl-piperidine; EPO <DP n="85"/> To a solution of l-(5-bromo-2-nitro-phenyl)-4-methyl-piperidine (0.60 g, 2.0 mmol) (as prepared in the previous step) in 5 mL of methanol was added bis(neopentylglycolato) diboron (0.68 g, 3.0 mmol), potassium acetate (0.40 g, 4.0mmol), and Pd(dppf)Cl2 (0.07 g, 5 mol%) and the reaction heated for 5 h at 60 0C. The solution was concentrated and the product eluted from a 20-g SPE cartridge (silica) with 100% DCM to give 0.46 g<70%) of the title compound as a red oil. 1H-NMR (400 MHz, CDCl3): 57.71 (d, IH), 7.59 (d, IH), 7.40 (dd, IH), 3.80 (s, 4H), 3.26 (m, 2H), 2.82 (m, 2H), 1.74 (m, 2H), 1.48 (m, 3H), 1.40 (s, 6H), 1.0 (d, 3H).

Reference： [1]Patent: WO2006/47504,2006,A1 .Location in patent: Page/Page column 83-84

23
[ 898825-59-7 ]
[ 201733-56-4 ]
[ 898825-60-0 ]

Yield	Reaction Conditions	Operation in experiment
84%	With potassium acetate;bis-triphenylphosphine-palladium(II) chloride; In dimethyl sulfoxide; at 50℃; for 4h;	A DMSO solution of the product bromide, potassium acetate (3 eq.), P(Ph)3Pd(II)Cl2 catalyst (0.05 eq.) and bis(neopentylglycolato)diboron (3 eq.) was heated at 50 C. under argon for 4 h. After 150 mL water and 150 mL ethyl acetate was added, the organic phase was separated. The aqueous phase was extracted one more time with 50 mL ethyl acetate. The organic phases were pooled and washed with water (2×), brine (2×) and dried (sodium sulfate). The solvent was evaporated and the residue was purified by filtering through a 400 mL silica pad using toluene-ethyl acetate gradient to get 4.4 g (84%) of the title compound MS: 285.08 (M+H+); 1H-NMR (DMSO-d6): delta (ppm) 8.47 (d, 1H, J=8.7 Hz), 8.33 (s, 1H), 7.97 (m, 1H), 7.88-7.79 (m, 2H), 2.69 (s, 3H), 2.64 (s, 3H).
		A mixture of 6-bromo-2-(2,4-dimethyl-thiazol-5-yl)-quinoline ( 15 g, 46.99 mmol), bis(neopentylglucolato)diboron (31.83 g, 141 mmol), bis(triphenylphosphine)-palladium (II) chloride (1.65 g, 2.35 mmol), and potassium acetate (13.81 g, 141 mmol) in anhydrous DMSO (260 mL) was stirred under Ar at 90 0C for 2 h then was cooled down to room temperate. The mixture was poured into water (1.2 L) and the precipitate were collected by filtration, washed with water, and dried. To the dried solid was added EtOAc (600 mL) and the insoluble solid was filtered off. The filtrate was evaporated and the product was adsorbed onto silica gel and purified by a short silica pad eluting with EtOAc-hexane (5:2) to give 2-(2,4-dimethyl-thiazol-5-yl)-quinoline-6-boronic acid (16.4 g, still containing about 30% bis(neopentyl glucolato)diboron indicated by NMR- 94% yield).

Reference： [1]Patent: US2006/293320,2006,A1 .Location in patent: Page/Page column 35
[2]Patent: WO2008/8912,2008,A1 .Location in patent: Page/Page column 97

24
[ 841297-65-2 ]
[ 201733-56-4 ]
2-(4'-chloro-4-methoxy-biphenyl-2-yl)-quinoline-6-boronic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With potassium acetate;bis-triphenylphosphine-palladium(II) chloride; In dimethyl sulfoxide; at 95℃; for 24h;	Preparation of 2-(4'-chloro-4-methoxy-biphenyl-2-yl)-quinoline-6-boronic acid 1.6 1.06 g (2.5 mmol) 1.5, 740 mg (7.5 mmol) potassium acetate, 87 mg (0.125 mmol) dichloro[1,1'-bis(triphenylphosphino)]palladium (II) dichloromethane adduct and 680 mg (3 mmol) bis(neopentyl glycolato)diboron were dissolved in 15 mL DMSO and the mixture was heated overnight at 95 C. for one day. The crude product was precipitated by addition of 30 mL water and purified on a silica gel pad using toluene-ethyl acetate solvent gradient elution to give 1.6 in quantitative yield. H1-NMR (CDCl3): delta (ppm) 8.27 (s, 1H), 8.16 (d, 1H, J=8.4 Hz), 7.98-7.89 (m, 2H), 7.40 (d, 1H, J=8.4 Hz), 7.25-7.02 (m, 7H), 3.85 (s, 3H).

Reference： [1]Patent: US2007/32488,2007,A1 .Location in patent: Page/Page column 19; 30

25
[ 55580-07-9 ]
[ 201733-56-4 ]
C₁₅H₂₁BO₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃;	IA: 4-(4-Boronophenoxy)-butyric acid; [00191] A resealable tube was charged with <strong>[55580-07-9]4-(4-bromophenoxy)butyric acid</strong>(259 mg, 1.0 mmol), 5,5,5',5'-Tetramethyl-[2,2']bi[[l,3,2]dioxaborinanyl] (249 mg, 1.1 mmol), potassium acetate (245 mg, 2.5 mmol), and DMSO (2 mL). The resulting orange suspension was deoxygenated by sparging with nitrogen gas. Dichloro[l,l '- bis(dipheirylphosphmo)ferrocene] palladmm(II) dichloromethane adduct (30 mg, 0.041 mmol) was added, and the tube was sealed tightly and heated at 800C overnight. Hydrochloric acid (IN) was added, and the mixture was extracted with EtOAc (2 x), washed with water (2 x) and brine (1 x), and dried (MgSO^. The organic layer was concentrated in vacuo and the residue purified by flash chromatography (0 to 15% MeOH in DCM) to give the 2,2-dimethyl- 1,3 -propanediol boronic ester of IA. This material was dissolved in diethyl ether and washed with NaOH (2 N, 2 x). The aqueous layers were washed with diethyl ether, combined, and acidified to pH 4 with hydrochloric acid (6 N). The resulting solid precipitate was collected by filtration to afford IA (210 mg, 94%) as a beige solid. 1H NMR (400 MHz, CD3OD) delta 2.06 (m, 2H), 2.48 (t, J = 7.5 Hz52H), 4.02 (t, J = 6.6 Hz, 2H), 6.88 (br s, 2H), 7.62 (br d, 2H).

Reference： [1]Patent: WO2007/76431,2007,A1 .Location in patent: Page/Page column 67

26
[ 35656-89-4 ]
[ 201733-56-4 ]
[ 943739-88-6 ]

Yield	Reaction Conditions	Operation in experiment
76%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃;	2A: 4-[4-(5,5-Dimethyl-[l,3,2]dioxaborinan-2-yl)-phenyl]-butyric acid; [00198] A resealable tube was charged with 4-bromophenyl butyric acid (729 mg, 3.1 mmol), 5,5,5',5?-Tetramethyl-[2,2?]bi[[l,3,2]dioxaborinanyl] (746 mg, 3.3 mmol), potassium acetate (736 mg, 7.5 mmol), and DMSO (4 mL). The resulting orange suspension was deoxygenated by sparging with nitrogen gas. Dichloro[l,l'- bis(diphenylphosphino)ferrocene] palladium(II) dichloromethane adduct (66 mg, 0.090 mmol) was added, and the tube was sealed tightly and heated at 80C overnight. Hydrochloric acid (IN) was added, and the mixture was extracted with EtOAc (2x), washed with water (2x) and brine (Ix), and dried (MgSO-).). The organic layer was concentrated in vacuo and the residue purified by flash chromatography (0 to 15% MeOH in DCM) to afford 2A (626 mg, 76%) as an off-white solid. 1H NMR (400 MHz, CDCl3) delta 1.02 (s, 6H), 1.97 (m, 2H), 2.36 (t, J = 7.5 Hz, 2H), 2.68 (t, J = 7.7Hz, 2H), 3.76 (s, 4H), 7.18 (d, / = 7.9 Hz, 2H), 7.72 (d, / = 7.5 Hz, 2H).

Reference： [1]Patent: WO2007/76431,2007,A1 .Location in patent: Page/Page column 71

27
[ 943740-08-7 ]
[ 201733-56-4 ]
[ 943740-09-8 ]

Yield	Reaction Conditions	Operation in experiment
57%		6D: 4-(4-(3-cyano-4-(ethylsulfonyl)phenylamino)-4-oxobutyl)phenylboronic acid; [00222] A flask containing 6C (83 mg, 0.19 mmol), 5,5,5',5'-tetramethyl-[2,2']bi[[l,3,2]dioxaborinanyl] (47.6 mg, 0.211 mmol), potassium acetate (83 mg, 0.84 mmol), and dichloro[l,F-bis(diphenylphosphino)ferrocene] palladium(II) dichloromethane adduct (4.4 mg, 0.0060 mmol) was purged with argon. DMSO (1 mL) was added, and the reaction mixture was degassed with three cycles of vacuum followed by argon backfill. The reaction mixture was heated for 2 h at 800C, cooled to rt, and diluted with water (100 mL). The aqueous solution was extracted with diethyl ether (3 x 25 mL), dried (MgSO4), and concentrated under reduced pressure. The residue was dissolved in a mixture of diethyl ether (1 mL), DCM (-0.1 mL), and EtOAc (~0.1 mL). Diethanolamine (22 mg, 0.21 mmol) in isopropanol (0.5 mL) was added, and the reaction mixture was stirred overnight at rt. The reaction mixture was concentrated, and the residue was purified by reverse phase HPLC (under the standard acidic conditions) to give 6D (44 mg, 57%) as a clear oil. MS (ESI) m/z 425.4 (M+CH3OH-H2O+H)+.

Reference： [1]Patent: WO2007/76431,2007,A1 .Location in patent: Page/Page column 82

28
[ 943742-46-9 ]
[ 201733-56-4 ]
[ 943742-47-0 ]

Yield	Reaction Conditions	Operation in experiment
72%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃; for 3h;	66C : 4-(2-(3-((benzyloxycarbonylamino)methyl)phenylamino)-2- oxoethoxy)phenylboronic acid; [00504] A sealed tube was charged with 66B (235 mg, 0.5 mmol), 5,5,5',5'-Tetramethyl-[2,2']bi[[l,3,2]dioxaborinanyl] (135 mg, 0.6 mmol), potassium acetate (98 mg, 1.25 mmol), and DMSO (2 mL). The resulting orange suspension was deoxygenated by sparging with nitrogen gas. Dichloro [1,1'- <n="224"/>bis(diphenylphosphino)ferrocene] palladium(II) dichloromethane adduct (30 mg, 0.041 mmol) was added, and the tube was sealed and heated at 80 C for 3 h. The reaction was quenched with water, then extracted with EtOAc (3x20 mL). The organic layer was washed with brine, dried (Na2SO^), filtered through a pad of silica gel and concentrated. The residue was purified via reverse phase HPLC to give 66C (157 mg, 72%). MS (ESI) m/z 435.4(M+H)+.

Reference： [1]Patent: WO2007/76431,2007,A1 .Location in patent: Page/Page column 221-222

29
[ 319474-34-5 ]
[ 201733-56-4 ]
[ 944956-50-7 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In ethanol; for 20h;Heating / reflux;	[306] 4-Iodo-7-Azaindole (1.0Og, 4.12mmol), bis(neopentylglycolato)diboron (1.49g, 6.59mmol), potassium acetate (0.65g, 6.59mmol), and l,r-bis(diphenylphosphino)ferrocene dichloro palladium (II) dichloromethane complex (0.09g, 0.12mmol) were added to a round bottom flask. The flask was evacuated and backfilled with N2 (3 x). Anhydrous ethanol (2OmL) was added and the mixture was heated to reflux for 2Oh. After cooling to rt, the reaction mixture was diluted with diethyl ether (35mL) and then filtered through celite. The resulting filtrate was concentrated in vacuo and dissolved in ethyl acetate (5OmL). The solution was washed with water (15mL), brine (15mL), and dried over MgSO4. The filtrate was concentrated to a brown solid which was recrystallized with ethyl acetate to yield the title compound as a tan solid. The mother liquor was concentrated in vacuo and purified by column chromatography (HexanesrEtOAc = 80:20 ? 60:40) to yield the title compound. 1H NMR (400 MHz, DMSO-d6) delta 0.99 (s, 6H), 3.83 (s, 4H), 6.69 (dd, IH3 J= 1.8, 1.0 Hz), 7.30 (d, IH, J = 2.4 Hz), 7.45 (dd, IH3 J= 2.8, 2.4 Hz), 8.18 (d, IH, J= 2.2 Hz), 11.52 (bs, IH).

Reference： [1]Patent: WO2007/84667,2007,A2 .Location in patent: Page/Page column 93-94

30
[ 50998-17-9 ]
[ 201733-56-4 ]
[ 946501-49-1 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; at 110℃; for 4h;	Step 2: 6-(5,5-Dimcthyl-l,3,2-dioxaborinan-2-yl)quinoxalinc (E2)A mixture of <strong>[50998-17-9]<strong>[50998-17-9]6-bromoquinoxalin</strong>e</strong> (1.0 eq.), bis-(neopentylglycolato)diborane (1.1 eq.), KOAc (3.0 eq.) and Pd(dppf)Cl2 (0.05 eq.) in 1,4-dioxane was degassed with a stream of Ar for 10 minutes and then heated at 11O0C for 4 hrs. The reaction mixture was concentrated and the residue used in the next step without further purification. MS (ES) Ci3H5BN2O2 requires: 242, found: 175 (M-[C5Hi0] +H+).

Reference： [1]Patent: WO2007/93827,2007,A1 .Location in patent: Page/Page column 47

31
[ 54675-23-9 ]
[ 201733-56-4 ]
[ 942120-42-5 ]
[ 942120-41-4 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In dimethyl sulfoxide; at 80℃; for 3h;	7C. 6-(5,5-dimethyl-l,3,2-dioxaborinan-2-yl)-4-hydroxyquinolin-2(lH)-one and 4-hydroxy-2-oxo-l,2-dihydroquinolin-6-ylboronic acid: To 7B(815 mg, 3.37 mmol) in DMSO (25 mL) was added 5,5,5',5'-tetramethyl-2,2'- bi(l,3,2-dioxabormane) (837 mg, 3.70 mmol), potassium acetate (500 mg, 5.06 mmol) and Pd(drhopf)Cl2»CH2Cl2 (74 mg, 0.10 mmol). The reaction was degassed and heated under argon at 80 0C for about 3 h. The reaction was cooled to rt and a precipitate formed. The solid was collected by filtration and purification by reverse phase HPLC (acetonitritrile/water/0.1%TFA) to give 0.655 g of 7C as a white solid. This was a ~2:1 mixture of boronate and boronic acid. For boronic acid: MS 206.0 (M+H)+. 1H NMR (400 MHz, DMSO-d6) for boronic acid: delta: 5.74 (s, 1 H) 7.20 (d, J=7.92Hz, 1 H) 7.88 (dd, J=8.35, 1.82 Hz, 1 H) 8.31 (s, 1 H). For boronate: delta: 0.96 (s, 6 H)) 3.76 (s, 4 H) 5.73 (s, 1 H) 7.22 (d, J=7.91Hz, 1 H) 7.76 (dd, /=8.35, 1.82 Hz, 1 H) 8.19 (s, 2 H).

Reference： [1]Patent: WO2007/70818,2007,A1 .Location in patent: Page/Page column 102

32
[ 20077-10-5 ]
[ 201733-56-4 ]
[ 777864-76-3 ]

Reference： [1]Journal of the American Chemical Society,2007,vol. 129,p. 12148 - 12158

33
[ 58534-94-4 ]
[ 201733-56-4 ]
[ 886854-88-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; for 16h;Heating / reflux;	A mixture of l-bromo-2-fluoro-3-nitrobenzene (800mg; 3.63mmol), bis(neopentyl glycolato)diboron (900mg; 3.98mmol), [l,l'-bis(diphenylphosphino)- ferrocene]dichlropalladium, 1:1 complex with dichloromethane (lOOmg; 0.12mmol), potassium acetate (1.0 g; 10.2mmol), and dioxane (2OmL) was heated at reflux for 16hr.[00299] The mixture is cooled to room temperature, treated with water(10OmL), and extracted with ethyl acetate (3 x 25mL). The extracts are washed with water (2 x 25mL) and brine (I x 25mL), dried over sodium sulfate, and concentrated in vacuo. The residue is purified by flash chromatography over silica gel (elution with ether/hexane 1/2) to give 2-(2-fluoro-3-nitro-phenyl)-5,5-dimethyl- [l,3,2]dioxaborinane as a pale yellow solid (350mg)

Reference： [1]Patent: WO2008/33858,2008,A2 .Location in patent: Page/Page column 207

34
[ 949891-80-9 ]
[ 201733-56-4 ]
[ 949892-15-3 ]

Yield	Reaction Conditions	Operation in experiment
65%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃; for 0.25h;Microwave irradiation;	Reference Example 21; 7-(5 , 5-Dimethyl[1 , 3 , 2]dioxaborinan-2-yl)-8-(5-fluoro-2-methylphenoxymethyl)-1,3,3-trimethyl-3,4-dihydro-1H-quinoxalin-2-one(ReferenceCompound21) A mixture of 7-bromo-8-(5-fluoro-2-methylphenoxymethyl)-1,3,3-trimethyl-3,4-dihydro-1H-quinoxalin-2-one (Reference Compound No.8-1, 98.7 mg, 0.242 mmol), bis(neopentyl glycolate)diboron (170 mg, 0.753 mmol), potassium acetate (112 mg, 1.14 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]palladium(II )dichloride dichloromethane complex (1 : 1) (20.7 mg, 0.0253 mmol) was suspended in dimethylsulfoxide (2 mL), and the reaction mixture was stirred at 80C for 15 minutes under microwave. After cooling down, ethyl acetate (15 mL) and water (15 mL) were added to the reaction mixture and partitioned. The organic layer was washed with saturated brine (15 mL), dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (1st : hexane-ethyl acetate, 2nd : chloroform). The obtained residue was filtered with hexane (5 ml) to give the titled reference compound (70.2 mg) as a colorless solid. (Yield 65%)

Reference： [1]Patent: EP1995242,2008,A1 .Location in patent: Page/Page column 50

35
[ 841297-65-2 ]
[ 201733-56-4 ]
[ 1165794-32-0 ]

Yield	Reaction Conditions	Operation in experiment
70%	With potassium acetate;tetrakis(triphenylphosphine) palladium(0); In dimethyl sulfoxide; at 50℃; for 3h;	Example 15: Synthesis of 18-[2-(4'-Chloro-4-methoxy-biphenyl-2-yl)-quinolin-6-yll- 17-cvclohexyl-1.4J l-triaza-tricvclori l.5.2.016'19licosa-7J3(20).14J6(19)J7- pentaene-3,12-dione (16)Step A.A mixture of 6-bromo-2-(4'-chloro-4-methoxy-biphenyl-2-yl)-quinoline (200 mg, 0.473 mmol, synthesized as reported in WO2006/076529), bis(neopentylglycolato)- diboron (127 mg, 1.2 eq), potassium acetate (90 mg, 2 eq) and tetrakis(triphenylphosphine)palladium(0) (0.11 eq) in DMSO was stirred at 500C under N2 during 3h. The reaction mixture was then diluted with ethyl acetate, washed with a NaHCOs solution (5 M) and with brine, then dried over Na2SO4, filtered and concentrated. The residue was purified by preparative TLC to afford 150 mg (70%) of 2-(4'-chloro-4-methoxy-biphenyl-2-yl)-6-(5,5-dimethyl-[l,3,2]dioxaborinan-2-yl)- quinoline 15-1; m/z = 458 (M+H+).

Reference： [1]Patent: WO2009/80836,2009,A2 .Location in patent: Page/Page column 87

36
[ 138647-49-1 ]
[ 201733-56-4 ]
[ 1167991-21-0 ]

Yield	Reaction Conditions	Operation in experiment
71%	With potassium phosphate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; toluene; at 20 - 110℃;	n-Butyllithium (924 ml_, 2.3 mol, 2.5 M in hexane) was added slowly to a solution of diisopropylamine (323.3 ml_, 3.2 mol) in THF (6 L) at -78 C and stirred for 1 h. A solution of tert-butyl 4-oxopiperidine-i-carboxylate (400 g, 2.01 mol) in THF (2 L) was added and the mixture was stirred for 1 h at -78 0C. A solution of lambda/-phenyltriflimide (753 g, 2.11 mol) in THF (2 L) was added at -78 0C and the reaction mixture was allowed to warm to rt and stirred at rt overnight. The reaction mixture was diluted with ethyl acetate and washed with brine, and the separated organic phase was dried over Na2SO4, filtered, and concentrated. The crude residue was purified by silica gel column chromatography (hexanes/ethyl acetate, 5:1) to afford tert-butyl 4- (trifluoromethylsulfonyloxy)-5,6-dihydropyridine-1 (2H)-carboxylate as a brown oil. To an oven dried flask containing tert-butyl 4-(trifluoromethylsulfonyloxy)- 5,6-dihydropyridine-1(2H)-carboxylate (12 g, 36.25 mmol), 2-(5,5-dimethyl- 1 ,3,2-dioxaborinan-2-yl)-5,5-dimethyl-1 ,3,2-dioxaborinane (9.82 g, 43.5 mmol) and K3PO4 (24.62 g, 116 mmol) were added toluene (100 mL) and dioxane (40 mL). While stirring the reaction mixture at room temperature, the air in the flask was removed and refilled with N2. This process was repeated three times, followed by the addition of [1 ,1'- Bis(diphenylphosphino)ferrocene]palladium(ll)chloride (4.89 g, 5.35 mmol) and the reaction mixture was stirred overnight at 110 0C, cooled to room temperature and filtered through a pad of Celite, and the filtrate was evaporated in vacuo. The dark red oily material was chromatographed on silica column (ethyl acetate/hexanes 4:96 to 10:90) to yield compound tert- Butyl-4-(5,5-dimethyl-1 ,3(2-dioxaborinan-2-yl)-5,6-dihydropyridine-1 [2H)- carboxylate (7.59 g, 71%) as an orange solid. 1H NMR (400 MHz, CDCI3) delta <n="42"/>6.41 (br. s, 1 H), 3.94 (s, 2H), 3.63 (s, 4H), 3.42 (s, 2H), 2.18 (s, 2H), 1.44 (s, 9H), 0.97 (s, 6H).

Reference： [1]Patent: WO2009/81259,2009,A1 .Location in patent: Page/Page column 34; 39-41
[2]Bioorganic and Medicinal Chemistry Letters,2010,vol. 20,p. 1114 - 1117

37
[ 1131042-09-5 ]
[ 201733-56-4 ]
C₂₆H₃₅BClN₃O₆ [ No CAS ]
[ 1131042-23-3 ]

Yield	Reaction Conditions	Operation in experiment
83%	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In tetrahydrofuran; at 75 - 78℃;Inert atmosphere;	Into a pressure bottle (75 ml.) were charged, 1 ,1-dimethylethyl (5-bromo-6- chloro-3-[(2S)-2-([(1 ,1-dimethylethyl)oxy]carbonyl}amino)-3-phenylpropyl]oxy}-2- pyridinyl)carbamate (2.30 g, 4.1 mmol), Pd(dppf)CI2CH2CI2 (0.33 g, 0.41 mmol), 5,5,5',5'-tetramethyl-2,2'-bi-1 ,3,2-dioxaborinane (1.2 g, 5.3 mmol), potassium acetate (1.2 g, 12 mmol), and THF (20 ml_). The mixture was purged with argon for 1 min, sealed, and heated at 75 C. After 5 h heating, additional 5, 5,5', 5'- tetramethyl-2,2'-bi-1 ,3,2-dioxaborinane (0.46 g) and Pd(dppf)CI2CH2CI2 (0.1 g) were added, and reaction mixture was stirred at 78 C for ca. 20 h. After cooling to room temperature, the mixture was concentrated in vacuo. The residue was purified by flash chromatography (eluant: 10% to 50% ethyl acetate gradient in hexane) to afford the title compound as a glassy solid (2.0 g, 83%), and was used <n="37"/>without further purification. MS(ES)+ m/e 464 [M+H+] (Boronic acid ion observed in Mass spec not parent ion). Note: This solid contains ca. 20% of the acetate product which results from transamidation with potassium acetate MS(ES)+ m/e 522 [M+H+]..

Reference： [1]Patent: WO2009/32651,2009,A1 .Location in patent: Page/Page column 8; 35-36

38
[ 1131041-74-1 ]
[ 201733-56-4 ]
C₂₈H₃₆BClN₄O₆ [ No CAS ]
[ 1131042-28-8 ]

Yield	Reaction Conditions	Operation in experiment
87%	With potassium acetate;Pd(ddpf)Cl2 with/without CH2Cl2; In tetrahydrofuran; at 70 - 85℃;Inert atmosphere;	Into a pressure bottle (150 mL) were charged, 5,5,5',5'-tetramethyl-2,2'-bi- 1 ,3,2-dioxaborinane (2.7 g, 12 mmol), Pd(ddpf) (0.8 g, 1 mmol), potassium acetate (2.9 g, 30 mmol) and 1 ,1 -dimethylethyl (5-bromo-6-chloro-3-[(2S)-2-([(1 ,1- dimethylethyl)oxy]carbonyl}amino)-3-(1 H-indol-3-yl)propyl]oxy}-2- pyridinyl)carbamate (6.0 g, 10 mmol) in THF (60 mL). The mixture was purged with nitrogen for 1 min, and then immediately sealed. The contents were stirred and heated at 85C for 7 h, and then at 70C overnight. The reaction mixture was allowed to cool to room temperature and poured onto a solution of 1 N sodium hydroxide/ice, and stirred for 30 min. The mixture was neutralized with 1 M hydrochloric acid and extracted with ethyl acetate (3x). The combined organic layers were dried over MgSO4, filtered and concentrated in vacuo. This residue was suspended in dichloromethane and hexanes to facilitate additional solid formation. The crude solid was dried under high vaccum and collected as 5.5 g (87%). This material was used without additional purification. MS(ES)+ m/e 561 [M+H]+ (Boronic acid ion observed in mass spec, not parent ion). Note:This solid is impure with ca. 30% of the acetate product which results from transamidation with potassium acetate, MS(ES)+ m/e 503 [M+H]+
		A mixture of 1t (43g, 72.3 mmol), 5,5,5',5'-tetramethyl-2,2'-bi-1 ,3,2-dioxaborinane (21.2g, 1.3 eq.), KOAc (10.6g, 1.5 eq), Pd(dppf)CI2CH2CI2 adduct (2.95g, 5%) and THF (dry, 300 mL) in a 1 L sealed flask was purged with N2, sealed and heated at 78 0C overnight (16 h). To this mixture were added 1i (31.6g, 1.2 eq.), Pd(dppf)CI2CH2CI2 adduct (2.95g, 5%) and 2N Na2CO3 (72 mL, 2 eq.). The resulting mixture was purged with N2, sealed and heated at 90 0C for 4 h. LCMS indicated the completion of the reaction. The reaction mixture was cooled to rt, and filtered on celite, which was rinsed with EtOAc. The combined filtrates were washed with H2O (2x), brine, and dried over Na2SO4. Removal of the solvent followed by flash column chromatography purification on silica gel column afforded 45.83g of 1ua, b, c, and d as a mixture of yellow-brownish foamy solid.

Reference： [1]Patent: WO2009/32651,2009,A1 .Location in patent: Page/Page column 40
[2]Patent: WO2009/32653,2009,A1 .Location in patent: Page/Page column 11; 44

39
[ 696-62-8 ]
[ 201733-56-4 ]
[ 213596-33-9 ]

Reference： [1]Angewandte Chemie - International Edition,2009,vol. 48,p. 5350 - 5354
Angew. Chem., Int. Ed.,2009,vol. 121,p. 5454 - 5458
[2]Journal of the American Chemical Society,2017,vol. 139,p. 607 - 610
[3]Patent: CN106632440,2017,A .Location in patent: Paragraph 0096-0100
[4]Organic Letters,2014,vol. 16,p. 4562 - 4565

40
[ 576-83-0 ]
[ 201733-56-4 ]
[ 214360-78-8 ]

Yield	Reaction Conditions	Operation in experiment
95%	With tris-(dibenzylideneacetone)dipalladium(0); 2-(2,6-dimethoxyphenyl)-1-methyl-3-(diphenylphosphino)-1H-indole; cesium acetate; In 1,4-dioxane; at 20 - 110℃; for 0.5h;Schlenk technique; Inert atmosphere;	In a 20 mL Schlenk tube,Tris (dibenzylideneacetone) dipalladium (0.0046 g, 0.005 mmol) and a ligand (palladium: ligand: 0.5 mol%: 4.0 mol%) were added followed by a magnetic force with a Teflon coating Stirring sticks,The system was replaced by nitrogen protection, 0.5 mL freshly distilled 1,4-dioxane was added,Stir well while stirring for 10 minutes to form a palladium complex.Then 2,4,6-triethylbenzene bromide (0.5 mmol) was added under nitrogen,Neopentyl glycol boronate (0.6 mmol) and cesium acetate (1.5 mmol) were added.Finally 1,4-dioxane solution (1 ml) was added and stirring was continued for 5 minutes at room temperature.The Schlenk tube was then placed in a preheated 110 C oil bath for 30 minutes. After the reaction is completed,After cooling the reaction tube to room temperature and detecting the consumption of the aryl chloride by thin layer chromatography, the reaction was stopped,About 10 ml of water was added to the system, about 10 ml of ethyl acetate was added, and the organic layer was subjected to gas chromatography.Thereafter, about 10 ml of ethyl acetate was further added in three to four times, and the organic phase was combined and concentrated under reduced pressure.Column chromatography products Neopentyl glycol 2,4,6-trimethylbenzeneboronate, isolated yield 95%

Reference： [1]Patent: CN104327106,2017,B .Location in patent: Paragraph 0029; 0030
[2]Angewandte Chemie - International Edition,2009,vol. 48,p. 5350 - 5354
Angew. Chem., Int. Ed.,2009,vol. 121,p. 5454 - 5458

41
[ 182344-70-3 ]
[ 201733-56-4 ]
[ 1167418-11-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; at 23 - 90℃;	Example 58. N-Boc-indole-5-boronic acid, neopentylglycol ester (S48)To iV-Boc-5-bromoindole (592 mg, 2.00 mmol, 1.00 equiv) in dioxane (10 mL) at 230C was added PdCl2(dppf)- CH2Cl2 (163 mg, 0.200 mmol, 0.100 equiv), bis(neopentylglycolato)diborone (497 mg, 2.20 mmol, 1.10 equiv), and KOAc (392 mg, 4.00 mmol, 2.00 equiv). After stirring for 6.0 hr at 900C, the reaction mixture was cooled to 23 0C and concentrated in vacuo. The residue was dissolved in CH2Cl2 and filtered through a plug of Celite. After the removal of CH2Cl2, the residue was purified by chromatography on silica gel eluting with hexanes/EtOAc 97:3 (v/v) to afford 609 mg of the title compound as a colorless solid (92% yield).R/= 0.45 (hexanes/EtOAc 9:1 (v/v)). NMR Spectroscopy: 1H NMR (500 MHz, CDCl3, 23 0C, delta): 8.16 (d, / = 7.5 Hz, IH), 8.08 (s, IH), 7.80 (d, / = 8.5 Hz, IH), 7.59 (d, / = 3.5 Hz, IH), 6.60 (d, /= 3.5 Hz, IH), 3.81 (s, 4H), 1.69 (s, 9H), 1.05 (s, 6H). 13C NMR (125 MHz, CDCl3, 23 0C, delta): 149.69, 136.96, 130.09, 129.72, 127.17, 126.10 (br), 125.61, 114.22, 107.59, 83.50, 72.25, 31.83, 28.11, 21.83. Mass Spectrometry: HRMS-FIA (m/z): Calcd for [M + H]+, 330.18712. Found, 330.18650.

Reference： [1]Organic Letters,2009,vol. 11,p. 2860 - 2863
[2]Patent: WO2010/59943,2010,A2 .Location in patent: Page/Page column 84; 85

42
[ 552330-38-8 ]
[ 864775-99-5 ]
[ 201733-56-4 ]
1,1-dimethylethyl [(1S)-2-[4-chloro-3-(3-methyl-1H-pyrazolo[3,4-b]pyridin-5-yl)phenyl]oxy}-1-(1H-indol-3-ylmethyl)ethyl]carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%		A mixture of solid 192 (e) (1.5g, 3.94 mmol), [1, 1'bis (diphenylphosphino) ferrocene] Dichlorophalladium (II) (173mg, 0. 236mol), 5,5, 5', 5'-tetramethyl-2, 2'-bi-1, 2,3- triborinane (1.06g, 4.72 mmol), potassium acetate (580mg, 5.91 mmol) and 20 ml dry dioxane was heated up to 80 C under nitrogen for overnight. To this reaction mixture was added compound 69 (a) (1.90g, 3.97 mmol), Pd (PPh3) 4 (220 mg, 0.19 mmol) and Na2CO3 (2M, 4. 4moi). The reaction was heated at 150C for 15 min in microwave. The reaction mixture was washed with EtOAc and was concentrated. The residue was purified by flash column chromatography to give 1.5g (75%) compound 192 (f)

Reference： [1]Patent: WO2005/85227,2005,A1 .Location in patent: Page/Page column 58; 158

43
18-(p-iodophenyl)octadecyl phosphocholine [ No CAS ]
[ 201733-56-4 ]
[ 1092072-73-5 ]

Yield	Reaction Conditions	Operation in experiment
81%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In methanol; at 50℃; for 2.5h;	Example 1; [0080] 18-[p-(Dihydroxyboryl)phenyl]octadecyl phosphocholine (2); [0081] NM404 (72 mg, 0.113 mmol), 6/s-(neopentylglycolato)diboron (60 mg, 0.266 mmol), anhydrous potassium acetate (34 mg, 0.346 mmol) and PdCl2(dppf) (5 mg, 0.0061 mmol) were placed in a 4 ml vial and dried under high vacuum for 30 min. The vial was filled with nitrogen and methanol (1.5 ml, degassed by three freeze - pump - thaw cycles) was added. Reaction mixture was stirred at 50 0C for 2 h, then evaporated, redissolved in chloroform and loaded onto silica gel column. The column was eluted first with stepwise gradient of CHCl3 - MeOH (90:10, 80:20, 50:50) and finally with CHCl3 - MeOH - H2O (65:25:4) to give the product as a white powder, 51 mg (81%). 1H-NMR (400 MHz, CDCl3 - CD3OD 1 :1): 7.53 and 7.19 (two d, J= 8 Hz, 2H each, C6H4), 4.26 - 4.20 (br m, 2H, POCH2CH2N), 3.87 (q, J= 6.6 Hz, 2H, CH2OPOCH2CH2N), 3.61 - 3.58 (m, 2H, CH2N), 3.22 (s, 9H, N(CH3)3), 2.61 (t, J= 7.7 Hz, 2H, ArCH2), 1.68 - 1.58 (m, 4eta, ArCH2CH2 and CH2CH2O), 1.42 - 1.24 (m, 28H, (CH2)i4). 13C- NMR (I OO MHZ5 CDCI3 - CD3OD 1:1): 144.82, 133.54, 127.93, 66.55 (m), 66.00 (d, Jc-P = 5.8 Hz), 58.95 (d, Jc-P = 5.1 Hz), 54.03 (t, Jc-N = 3.9 Hz), 36.03, 31.43, 30.85 (d, Jc-P = 7.6 Hz), 29.75 (four carbons), 29.71 (five carbons), 29.63, 29.54, 29.47, 29.33, 25.88. Due to the quadrupolar relaxation, the carbon attached to boron is not detected.

Reference： [1]Patent: WO2008/150439,2008,A1 .Location in patent: Page/Page column 27

44
[ 6329-74-4 ]
[ 201733-56-4 ]
[ 1229442-36-7 ]

Yield	Reaction Conditions	Operation in experiment
33%	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; 1,1'-bis(diphenylphosphino)ferrocene; In 1,4-dioxane; at 90℃; for 18h;Inert atmosphere;	In a Schlenk tube, a mixture of <strong>[6329-74-4]5-bromo-2-hydroxybenzamide</strong> (1.0 g, 4.63 mmol), bis(neopentylglycolato)diboron (2.09 g, 9.26 mmol) and potassium acetate (1.6 g, 13.9 mmol) was dissolved in dioxane (40 mL). The mixture was purged (vacuum-argon three times) and [1,1-Bis(diphenylphosphino)ferrocene]dichloro-palladium(II) dichloromethane complex (0.19 g, 0.23 mmol) and 1,1'-bis(diphenyl-phospheno)ferrocene (0.13 g, 0.23 mmol) were added. The mixture was purged again (vacuum-argon three times) and stirred at 90 C for 18 h. The suspension was removed by filtration and the filtrated diluted with water and extracted three times with ethyl acetate. The combined organic layers were washed with water, brine, and dried over anhydrous sodium sulphate. The solvent was removed in vacuum and the residue was purified by the SP1 automated purification system to give 0.4 g (1.54 mmol, 33%) of the title compound HPLC/MS (9 min) retention time 3.49 min. LRMS: m/z 180 (M-1)

Reference： [1]Patent: EP2196465,2010,A1 .Location in patent: Page/Page column 30

45
[ 93-44-7 ]
[ 201733-56-4 ]
[ 135-19-3 ]
[ 627906-96-1 ]

Reference： [1]Chemistry - A European Journal,2011,vol. 17,p. 786 - 791
[2]Chemistry Letters,2015,vol. 44,p. 366 - 368

46
[ 856677-05-9 ]
[ 201733-56-4 ]
N-({(5S)-3-[4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-3-fluorophenyl]-2-oxo-1,3-oxazolidin-5-yl}methyl)acetamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
50%	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In N,N-dimethyl-formamide; at 100℃; for 72h;Inert atmosphere;	Step A: N- (5SV3-r4-(5.5-dimethyl-1.3.2-dioxaborinan-2-vn-3-fluoroDhenyll-2-oxo-1.3- oxazolidin-5-yl}methyl)acetamideN-[(5S)-3-(4-bromo-3-fluorophenyl)-2-oxo-1 ,3-oxazolidin-5- yl]methyl}acetamide (500mg, 1 .51 mmmol) was weighed into a 20ml_ vial, followed by the addition of bis(neopentyl glycolato) diboron (619mg, 1.81 mmol), potassium acetate (593mg, 6.04mmol) and [1 , 1'-bis-(diphenylphosphino)ferrocene]-dichloropalladium (II) dcm complex (1 16mg, 0.151 mmol). The reaction mixture was purged with vacuum and backfilled with nitrogen three times. To this was added N,N dimethyl formamide(10ml_). The reaction was heated at 100C for 72 hours, cooled to ambient temperature,filtered through celite (~1 inch), and the celite was washed with additional ethyl acetate(100ml_). The combined organics were then concentrated in vacuo. The residue was dissolved in ethyl acetate (100ml_) and organic phase was washed with water (25ml_). The aqueous layer was extracted with additional ethyl acetate (100ml_). The combined organics were then washed with brine (2x50ml_), dried (MgS04), filtered, andconcentrated in vacuo. The crude material was purified by chromatography on silica gel (gradient: 80:20 hexanes:ethyl acetate) to afford the title compound as a light red solid (274mg, 50%). MS (APCI) m/z 604.3 (M+1 ) 1 H NMR (400 MHz, CHLOROFORM-d) delta ppm 1 .04 (s, 6 H) 2.01 - 2.04 (m, 3 H) 3.56 - 3.68 (m, 2 H) 3.69 - 3.78 (m, 2 H) 3.80 (s, 3 H) 4.07 (t, J=8.98 Hz, 1 H) 4.73 - 4.85 (m, 1 H) 6.03 (br. s., 1 H) 7.20 (dd, J=8.20, 2.15 Hz, 1 H) 7.37 (dd, J=11 .91 , 2.15 Hz, 1 H) 7.73 (dd, J=8.20, 7.23 Hz, 1 H).

Reference： [1]Patent: WO2011/45703,2011,A2 .Location in patent: Page/Page column 65

47
[ 1089680-12-5 ]
[ 201733-56-4 ]
[ 199858-19-0 ]

Yield	Reaction Conditions	Operation in experiment
80%	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In dimethyl sulfoxide; at 80℃; for 2.5h;	Reference Example 7 2-Methoxy-4-methoxymethoxyphenylboronic acid (Reference Compound No.7) A mixture of 2-iodo-5-methoxymethoxyanisole (Reference Compound No.6, 100 mg, 0.340 mmol), bis(neopentylglycolato)diboron (115 mg, 0.509 mmol), potassium acetate (66.7 mg, 0.680 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]palladium(II)dichlori de dichloromethane complex (1 : 1) (27.8 mg, 0.034 mmol) was suspended in dimethylsulfoxide (1.5 mL), and the mixture was stirred at 80C for 2.5 hours. After cooling down, ethyl acetate (100 mL) and water (100 mL) were added to the reaction mixture and partitioned. The organic layer was washed with saturated brine (50 mL), dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure. The obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate) to give the titled reference compound (57.6 mg) as a colorless solid. (Yield 80%)

Reference： [1]Patent: EP2327699,2011,A1 .Location in patent: Page/Page column 24

48
[ 1312478-59-3 ]
[ 201733-56-4 ]
[ 1312478-61-7 ]

Yield	Reaction Conditions	Operation in experiment
71%		Neopentyl diboron (9.4 g, 28 mmol), KOAc (7.1 g, 69 mmol, 3 eq.) and Pd(dppf)CI2 (532 mg, 0.69 mmol, 0.03 eq.) was added into a 200 mL round bottom flask equipped with a magnetic stirrer and a 120 mL addition funnel. The product of Step B of Preparation 2B, (2R)-4-(4-iodo-2-oxopyridin-1 (2H)-yl)-2-methyl-2-(methylsulfonyl)butanoic acid T5 (9.2 g, 23 mmol, 1.0 equiv.) was added into the addition funnel. The system was purged with nitrogen/vacuum and kept under nitrogen. Degassed DMSO (45 mL) was added into the addition funnel. The system was again purged with N2 for 5 mins. The T5 solution was added to the reaction mixture over 2 mins at room temperature then heated to 80C and maintained at that temperature for a further hour. The reaction mixture was cooled to RT and poured into 100 mL water. Mixture was adjusted to pH 3 with 6 N HCI and refrigerated for 30 min. A dark solid formed and was collected via filtration and dried under high vacuum over P2Os for 3 days to yield 13 g of solid product. The solid was suspended in 100 mL MeOH, 16 g silica gel was added and mixture was concentrated in vacuo. The preabsorbed material was packed into a cartridge, loaded onto an 80 g silica gel column and purified using 0 to 20% MeOH in DCM (product eluted out at -8% MeOH) in 45 min at 60 mL/min flow rate. The desired fractions were concentrated to furnish 6.3 g off white solid (71 %). LCMS m/z 318.0 (M - neopentyl + H), 396.1 (M - neopentyl + DMSO + H); 1H NMR (400 MHz, DMSO-d6) delta ppm 0.93 (s, 6 H) 1.54 (s, 3 H) 2.14 (ddd, J=13.04, 10.69, 4.79 Hz, 1 H) 2.38 (ddd, J=13.18, 10.45, 5.86 Hz, 1 H) 3.16 (s, 3 H) 3.73 (s, 4 H) 3.77 - 3.92 (m, 1 H) 4.05 (ddd, J=12.40, 10.74, 4.98 Hz, 1 H) 6.33 (dd, J=6.74, 1.27 Hz, 1 H) 6.62 (s, 1 H) 7.59 (d, J=6.84 Hz, 1 H) 13.87 (br. s., 1 H).

Reference： [1]Patent: WO2011/73845,2011,A1 .Location in patent: Page/Page column 35

49
[ 10403-47-1 ]
[ 201733-56-4 ]
[ 1329166-69-9 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In dimethyl sulfoxide; at 80℃; for 4h;Inert atmosphere;	To a flame-dried flask, equipped with a reflux condensor, containing 2- bromo-5-nitroaniline (10.0 g, 46.1 mmol), bis(neopentyl glycolato)diboron (13.01 g, 57.6 mmol), potassium acetate (13.57 g, 138 mmol), and PdC^dppf -CH^C^ adduct (0.941 g, 1.152 mmol) was added DMSO (132 mL). The resulting dark red-brown suspension was degassed with argon for 30 min. and then the reaction was warmed to 80 C. After 4 h, the reaction was stopped and cooled to rt. The reaction was poured slowly into vigorously stirred ice-cold water (300 mL) to give a brown suspension. After stirring for 10 min, the suspension was filtered to collect the solid. The solid was rinsed with water (3 x 125 mL), air-dried, and then dried under a vacuum to give a brown solid.Purification by normal phase chromatography gave 4.36 g of Intermediate 12 as an orange solid. MS (ESI) m/z: 183.1 (M-C5H8+H)+.
4.36 g	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In dimethyl sulfoxide; at 80℃; for 4.5h;Inert atmosphere;	To a flame-dried flask, equipped with a reflux condenser, containing 2-bromo- 5-nitroaniline (10.0 g, 46.1 mmol), bis(neopentyl glycolato)diboron (13.01 g, 57.6 mmol), potassium acetate (13.57 g, 138 mmol), and PdCl2(dppf)-CH2Cl2 adduct (0.941 g, 1.152 mmol) was added DMSO (132 mL). The resulting dark red-brown suspension was degassed with argon for 30 min and then the reaction was warmed to 80 C. After 4 h, the reaction was stopped and cooled to rt. The reaction was poured slowly into vigorously stirred ice-cold water (300 mL) to give a brown suspension. After stirring for 10 min, the suspension was filtered to collect the solid. The solid was rinsed with water (3x125 mL), air-dried, and then dried under a vacuum to give a brown solid. Purification by normal phase chromatography gave 4.36 g of Intermediate 12 as an orange solid. MS (ESI) m/z: 183.1 (M-C5H8+H)+.
4.36 g	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In dimethyl sulfoxide; at 80℃; for 4h;Inert atmosphere;	[00428] To a flame-dried flask, equipped with a reflux condenser, containing 2-bromo- 5-nitroaniline (10.0 g, 46.1 mmol), bis(neopentyl glycolato)diboron (13.01 g, 57.6 mmol), potassium acetate (13.57 g, 138 mmol), and PdCl2(dppf)-CH2Ci2 adduct (0.941 g, 1.152 mmol) was added DMSO (132 mL). The resulting dark red-brown suspension was degassed with argon for 30 min and then the reaction was warmed to 80 C. After 4 h, the reaction was stopped and cooled to rt. The reaction was poured slowly into vigorously stirred ice-cold water (300 mL) to give a brown suspension. After stirring for 10 min, the suspension was filtered to collect the solid. The solid was rinsed with water (3x125 mL), air-dried, and then dried under a vacuum to give a brown solid. Purification by normal phase chromatography gave 4.36 g of Intermediate 49 as an orange solid. MS(ESI) m/z: 183.1 (M-C5H8+H)+.

4.36 g	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In dimethyl sulfoxide; at 80℃; for 4.5h;Inert atmosphere;	To a flame-dried flask, equipped with a reflux condenser, containing 2-bromo-5-nitroaniline (10.0 g, 46.1 mmol), bis(neopentylglycolato)diboron (13.01 g, 57.6 mmol), potassium acetate (13.57 g, 138 mmol),and PdCl2(dppf)-CH2Cl2 adduct (0.941 g, 1.152 mmol) was added DMSO (132 mL).The resulting dark red-brown suspension was degassed with argon for 30 min and then the reaction was warmed to 80 C. After 4 h, the reaction was stopped and cooled to rt. The reaction was poured slowly intovigorously stirred ice-cold water (300 mL) to give abrown suspension. After stirring for 10 min, the suspension was filtered tocollect the solid. The solid was rinsed with water (3x125 mL), air-dried, andthen dried under a vacuum to give a brown solid. Purification by normal phase chromatography gave 4.36 g of Intermediate 14 as an orange solid
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In dimethyl sulfoxide; at 80℃; for 4h;Inert atmosphere;	To a round bottom flask containing 2-bromo-5-nitroaniline (5 g, 23.04 mmol), bis(neopentyl glycolato)diboron (6.51 g, 28.8 mmol), potassium accetate (6.78 g, 69.1 mmol), and 1,1?- bis(diphenylphosphino)ferrocene-Palladium (II) dichloride DCM complex (0.470 g, 0.576mmol), was added DMSO (80 mL). The resulting suspension was degassed with N2 for 30mm, and then reaction was warmed to 80C (under N2). After 4 hours, the reaction was stopped and cooled to r.t. The reaction was poured slowly to vigorously stirred ice-cold water (150 mL) to give a suspension. After stirring for 10 mm, the suspension was filtered to collect the solid. The solid was rinsed with water (3x5OmL), air dried and then dried under a vacuum to give the crudeproduct. The crude product was purified by flash column chromatography on silica gel (0-100% EtOAc in hexane) to give the title compound. LC/MS = 183 (M-C5H8+1).

Reference： [1]Journal of Medicinal Chemistry,2020
[2]Patent: WO2011/100401,2011,A1 .Location in patent: Page/Page column 142
[3]Patent: WO2013/22814,2013,A1 .Location in patent: Paragraph 00337
[4]Patent: WO2013/22818,2013,A1 .Location in patent: Paragraph 00428
[5]Patent: JP2015/528022,2015,A .Location in patent: Paragraph 0300
[6]Patent: WO2017/74833,2017,A1 .Location in patent: Page/Page column 29; 30

50
[ 1338254-66-2 ]
[ 201733-56-4 ]
[ 1338254-63-9 ]

Yield	Reaction Conditions	Operation in experiment
72%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dichloromethane; dimethyl sulfoxide; at 20 - 90℃;Inert atmosphere;	To a mixture of the aromatic halide (1.0 mmol; 1.0 eq.), bis(neopentyl glycolato)diboron (1.2 eq.), AcOK (3.0 eq.) and [l, -bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with DCM (0.1 eq.) in a glass vial, under inert atmosphere (Ar), is added degassed DMSO (5.0 mL). The resulting reaction mixture is purged at rt with N2 for 5 min, stirred at 90C and monitored by LC-MS. Upon reaction completion, the reaction mixture is concentrated under reduced pressure, the residue diluted with 9: 1 DCM/MeOH and a sat. aq. NH4C1 solution is added. The layers are separated and the aq. layer is extracted with 9: 1 DCM/MeOH (3x). The combined org. layers are dried over MgS04, filtered and concentrated under reduced pressure. Purification of the residue gives the desired product.Starting from the compound of Example 1 (679 mg), and proceeding in analogy to Procedure AO, the title compound was obtained, after purification by CC (DCM/MeOH 100:0 to 96:4) followed by trituration in EA, as a yellow solid (544 mg; 72% yield).1H NMR (d6-DMSO) delta: 9.12 (d, J = 0.5 Hz, 1H); 9.03 (s, 1H); 8.67 (s, 1H); 7.90 (d, J = 7.0 Hz, 1H); 7.53 (t, J = 5.2 Hz, 1H); 7.16 (dd, J = 7.0, 0.7 Hz, 1H); 3.82 (s, 4H);3.24- 3.13 (m, 2H); 2.67 (s, 3H); 1.09 (t, J = 7.2 Hz, 3H); 1.00 (s, 6H). MS (ESI, m z): 274.00 [M+H+ of the corresponding boronic acid].
72%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dichloromethane; at 20 - 90℃;Inert atmosphere;	To a mixture of the aromatic halide (1.0 mmol; 1.0 eq.), bis(neopentyl glycolato)diboron (1.2 eq.), AcOK (3.0 eq.) and [1,1?-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with DCM (0.1 eq.) in a glass vial, under inert atmosphere (Ar), is added degassed DMSO (5.0 mL). The resulting reaction mixture is purged at rt with N2 for 5 min, stirred at 90 C. and monitored by LC-MS. Upon reaction completion, the reaction mixture is concentrated under reduced pressure, the residue diluted with 9:1 DCM/MeOH and a sat. aq. NH4Cl solution is added. The layers are separated and the aq. layer is extracted with 9:1 DCM/MeOH (3×). The combined org. layers are dried over MgSO4, filtered and concentrated under reduced pressure. Purification of the residue gives the desired product.Preparation X 1-[5-(5,5-dimethyl-[1,3,2]dioxaborinan-2-yl)-8-methyl-isoquinolin-3-yl]-3-ethyl-urea Starting from the compound of Example 1 (679 mg), and proceeding in analogy to Procedure AO, the title compound was obtained, after purification by CC (DCM/MeOH 100:0 to 96:4) followed by trituration in EA, as a yellow solid (544 mg; 72% yield). 1H NMR (d6-DMSO) delta: 9.12 (d, J=0.5 Hz, 1H); 9.03 (s, 1H); 8.67 (s, 1H); 7.90 (d, J=7.0 Hz, 1H); 7.53 (t, J=5.2 Hz, 1H); 7.16 (dd, J=7.0, 0.7 Hz, 1H); 3.82 (s, 4H); 3.24-3.13 (m, 2H); 2.67 (s, 3H); 1.09 (t, J=7.2 Hz, 3H); 1.00 (s, 6H). MS (ESI, m/z): 274.00 [M+H+ of the corresponding boronic acid].

Reference： [1]Patent: WO2011/121555,2011,A1 .Location in patent: Page/Page column 119
[2]Patent: US2013/96119,2013,A1 .Location in patent: Paragraph 0726; 0881; 0882; 0883
[3]Journal of Medicinal Chemistry,2017,vol. 60,p. 3755 - 3775

51
[ 72835-25-7 ]
[ 201733-56-4 ]
[ 1352304-52-9 ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 115 - 118
[2]Journal of the American Chemical Society,2012,vol. 134,p. 115 - 118

52
[ 38803-30-4 ]
[ 201733-56-4 ]
[ 1352304-48-3 ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 115 - 118
[2]Journal of the American Chemical Society,2012,vol. 134,p. 115 - 118

53
[ 6476-32-0 ]
[ 201733-56-4 ]
[ 1352304-49-4 ]

Reference： [1]Journal of the American Chemical Society,2012,vol. 134,p. 115 - 118
[2]Journal of the American Chemical Society,2012,vol. 134,p. 115 - 118

54
[ 122008-78-0 ]
[ 201733-56-4 ]
(R)-butyl 2-(4-(4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-2-fluorophenoxy)phenoxy)propanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With 1,4-diaza-bicyclo[2.2.2]octane; di-mu-chloro-bis(1,5-cyclooctadiene)dirhodium; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In toluene; at 100℃; for 96h;Sealed tube;	According to the literature method (Tobisu, M. Kinuta, H. Kita, Y. Rmond, E. Chatani, N.J. Am. Chem. Soc. 2012, 134, 115-118), Under anhydrous and anaerobic conditions, cyhalofop-butyl (1.0 g, 2.8 mmol), bis (neopentylglycolato) diboron (1.9 g, 8.4 mmol), [RhCl(cod)] 2 (69 mg, 0.14 mmol) were added to a 25 mL sealed tube. Xantphos (324 mg, 0.56 mmol), DABCO (628 mg, 5.6 mmol), and freshly distilled toluene (5.6 mL).After sealing the plug, the mixture was heated to 100 C and stirred for 96 hours (oil bath).After the reaction was cooled to room temperature, ethyl acetate was diluted and filtered over Celite, and the filtrate was concentrated to silica gel column chromatography (hexane/ethyl acetate = 6:1 to 3:1) to afford 55a (1.02 g, yield: 82%) .

Reference： [1]Nature Chemistry,2017,vol. 9,p. 918 - 923
[2]Patent: CN108341739,2018,A .Location in patent: Paragraph 0323; 0324; 0325; 0326
[3]Journal of the American Chemical Society,2012,vol. 134,p. 115 - 118
[4]Journal of the American Chemical Society,2012,vol. 134,p. 115 - 118

55
[ 1214329-07-3 ]
[ 201733-56-4 ]
[ 1373126-40-9 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium acetate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In 1,4-dioxane; at 85℃; for 6.0h;	Step 2. Synthesis of ethyl 4-(4-chloro-1H-imidazol-1-yl)-6-methoxypyridine-2-carboxylate (C34) 1,1-Bis(diphenylphosphino)ferrocene-palladium(II) dichloride-dichloromethane complex (49.8 mg, 0.068 mmol) was added to a solution of ethyl 5-bromo-6-methoxypyridine-2-carboxylate (prepared in analogous fashion to <strong>[1214329-07-3]methyl 5-bromo-6-methoxypyridine-2-carboxylate</strong> (C30) in Preparation 10 ; 254 mg, 0.97 mmol), 5,5,5',5'-tetramethyl-2,2'-bi-1,3,2-dioxaborinane (264 mg, 1.17 mmol), and potassium acetate (293 mg, 2.92 mmol) in 1,4-dioxane (8 mL). The reaction was stirred at 85 C. for 6 hours, whereupon it was allowed to cool to room temperature. Dichloromethane was added, and the resulting mixture was washed with saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate, and concentrated in vacuo to afford intermediate ethyl 5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-6-methoxypyridine-2-carboxylate. To a solution of ethyl 5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-6-methoxypyridine-2-carboxylate (crude) in methanol (50 mL) was added 4-chloro-1H-imidazole (C33) (100 mg, 0.97 mmol) and copper(I) oxide (14 mg, 0.098 mmol) and the reaction was stirred at ambient temperature overnight. The mixture was heated to 50 C. for 2 hours, and additional copper(I) oxide (14 mg, 0.098 mmol) was added. The reaction was heated to reflux for 2 hours and was then filtered through Celite. The Celite pad was washed with methanol, and the combined filtrate and washings were concentrated in vacuo. Purification was carried out twice via silica gel chromatography (Gradient: 0% to 50% ethyl acetate in heptane, then 0% to 40% ethyl acetate in heptane), affording the title compound as a white solid. Yield: 29.3 mg, 0.104 mmol, 11%. LCMS m/z 282.1 (M+1). 1H NMR (400 MHz, CDCl3) delta 1.44 (t, J=7.1 Hz, 3H), 4.14 (s, 3H), 4.46 (q, J=7.1 Hz, 2H), 7.24 (d, J=1.6 Hz, 1H), 7.67 (d, J=7.8 Hz, 1H), 7.82-7.83 (m, 1H), 7.84 (d, J=7.8 Hz, 1H).

Reference： [1]Patent: US2012/252758,2012,A1 .Location in patent: Page/Page column 30

56
[ 1122-91-4 ]
[ 201733-56-4 ]
[ 128376-65-8 ]

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 6230 - 6235,6

57
[ 460-00-4 ]
[ 201733-56-4 ]
[ 225916-39-2 ]

Yield	Reaction Conditions	Operation in experiment
84%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In toluene; at 80℃; for 2h;Inert atmosphere;	To a stirred solution of 1-bromo-4-fluorobenzene (20 g, 114 mmol), bis(neopentyl glycolato)diboron (31.0 g, 137 mmol) and potassium acetate (33.6 g, 343 mmol) in toluene (200 mL) was purged argon for 20 min. PdCl2 (dppf).CH2Cl2 Adduct (2.80 g, 3.43 mmol) was added and purged argon for 5 min. The reaction mixture was heated to 80 C. and maintained for 2 h. Reaction mixture was cooled to room temperature and it was concentrated under reduced pressure. The crude was dissolved in EtOAc (300 mL), filtered through a pad of CELITE and rinsed with EtOAc (100 mL), filtrate was washed with water (200 mL) followed by brine (100 mL). The organic layers were mixed and dried over anhydrous sodium sulfate. Organic layer was concentrated under reduced pressure. Purification via flash chromatography gave 168B (off-white solid, 21 g, 96 mmol, 84% yield). 1H NMR (400 MHz, DMSO-d6) delta 7.75-7.71 (m, 2H), 7.18-7.13 (m, 2H), 3.75 (s, 4H), 0.95 (s, 6H).

Reference： [1]Patent: US2016/289171,2016,A1 .Location in patent: Paragraph 0807
[2]Tetrahedron Letters,2012,vol. 53,p. 6230 - 6235,6

58
[ 13720-06-4 ]
[ 201733-56-4 ]
[ 1067188-97-9 ]

Yield	Reaction Conditions	Operation in experiment
31%	With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In dimethyl sulfoxide; at 80℃; for 21h;Inert atmosphere;	Synthesis Example 4: Production of Compound (11a) having boronic acid or ester thereof group To a 20-mL round-bottom flask containing a stirring bar were added <strong>[13720-06-4]2,6-dibromonaphthalene</strong> (115.4 mg, 0.40 mmol), bis(neopentyl glycol)diboron (273.3 mg, 1.2 mmol), (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II) (10.3 mg, 13 mumol), and potassium acetate (KOAc) (244.8 mg, 2.5 mmol), and argon gas was introduced into the flask. Dry dimethylsulfoxide (2 mL) was added thereto, and the resulting mixture was reacted at 80C for 21 hours while stirring. Subsequently, the mixture (reaction product) in the flask was cooled to room temperature and passed through silica gel. After the solvent was distilled off from the filtrate under reduced pressure using an evaporator, the residue (concentrate) was recrystallized from hexane to yield a white solid (47.8 mg). This white solid was identified by nuclear magnetic resonance (1H-NMR) analysis and mass spectrometry as a compound represented by the following General Formula (11a) : [Show Image] The yield of this compound was 31%. This compound was referred to as (11a). 1H NMR (400 MHz, CDCl3) delta1.06 (s, 12H), 3.83 (s, 8H), 7.83 (s, 4H), 8.33 (s, 2H). LRMS (EI) m/z calcd for C20H26B2O4 [M]+: 352, found 352.

Reference： [1]Patent: EP2537824,2012,A1 .Location in patent: Page/Page column 41-42

59
[ 1452573-07-7 ]
[ 201733-56-4 ]
[ 1452573-24-8 ]

Yield	Reaction Conditions	Operation in experiment
89%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 55℃; for 7h;Inert atmosphere;	[6- [2- [methyl- [(2-methylpropan-2-yl)oxycarbonyl] amino] propanoylamino] -2- [2-tri(propan-2-yl)silylethynyl] pyridin-3-yl] boronic acid A mixture of tert-butyl-N-[l-[[5-bromo-6-[2-tri(propan-2-yl)silylethynyl]pyridin-2-yl]- amino]-l-oxopropan-2-yl]-N-methylcarbamate CI (53 g, 98 mmol), bis(neopentyl glycolato)diboron (44.5 g, 197 mmol), KOAc (29 g, 295 mmol), 1 , 1 '-Bis(diphenyl- phosphino)ferrocene]dichloropalladium(II) (2.16 g, 2.95 mmol) and dioxane (250 ml) is stirred under argon atmosphere for 7 h at 55C. The mixture is diluted with DCM and extracted with a saturated aqueous solution of NaHC03. The combined organic layers are dried over MgSC^ and concentrated in vacuo. The product is purified by NP chromatography. Yield: 44 g (89%). HPLC-MS: M+H = 504; tR = 1.67 min (Method l).
48%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 50℃; for 17h;	A mixture of tert-butyl-N-[l-[[5-bromo-6-[2-tri(propan-2-yl)silylethynyl]pyridin-2-yl]- amino]-l-oxopropan-2-yl]-N-methylcarbamate Cla (51 g, 90 mmol), bis(neopentyl glycolato)diboron (40.5 g, 179 mmol), KOAc (26.4 g, 269 mmol), 1 , 1 '-Bis(diphenyl- phosphino)ferrocene]dichloropalladium(II) (3.3 g, 4.5 mmol) and dioxane (400 ml) is stirred under argon atmosphere for 17 h at 50C. The mixture is diluted with DCM and extracted with a saturated aqueous solution of NaHC03. The combined organic layers are dried over MgSC^ and concentrated in vacuo. The product is purified by NP chromatography. Yield: 21.9 g (48%). HPLC-MS: M+H=504; tR=2.17 min (*Method_4).
48%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 50℃; for 17h;Inert atmosphere;	D1a) [6-[2-[methyl-[(2-methylpropan-2-yl)oxycarbonyl]amino]propanoylamino]-2-[2-tri(propan-2-yl)silylethynyl]pyridin-3-yl]boronic acid A mixture of tert-butyl-N-[1-[[5-bromo-6-[2-tri(propan-2-yl)silylethynyl]pyridin-2-yl]-amino]-1-oxopropan-2-yl]-N-methylcarbamate C1a (51 g, 90 mmol), bis(neopentyl glycolato)diboron (40.5 g, 179 mmol), KOAc (26.4 g, 269 mmol), 1,1'-Bis(diphenyl-phosphino)ferrocene]dichloropalladium(II) (3.3 g, 4.5 mmol) and dioxane (400 ml) is stirred under argon atmosphere for 17 h at 50 C. The mixture is diluted with DCM and extracted with a saturated aqueous solution of NaHCO3. The combined organic layers are dried over MgSO4 and concentrated in vacuo. The product is purified by NP chromatography. Yield: 21.9 g (48%). HPLC-MS: M+H=504; tR=2.17 min (*Method-4).

Reference： [1]Patent: WO2016/23858,2016,A1 .Location in patent: Page/Page column 36-37
[2]Patent: WO2013/127729,2013,A1 .Location in patent: Page/Page column 57
[3]Patent: US2013/225567,2013,A1 .Location in patent: Paragraph 0278; 0279

60
[ 1452573-08-8 ]
[ 201733-56-4 ]
[ 1452573-25-9 ]

Yield	Reaction Conditions	Operation in experiment
75%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dimethyl sulfoxide; at 65℃; for 39h;Inert atmosphere;	A mixture of tert-butyl-N-[l-[[5-bromo-6-(2-phenylethynyl)pyridin-2-yl]amino]-l-oxo- propan-2-yl]-N-methylcarbamate C2a (2.5 g, 5.45 mmol), bis(neopentyl glycolato)diboron (2.46 g, 10.9 mmol), KOAc (1.61 g, 16.4 mmol), l, -Bis(diphenylphosphino)ferrocene]- dichloropalladium(II) (399 mg, 0.55 mmol) and DMSO (20 ml) is stirred under argon atmosphere for 39 h at 65C. The mixture is diluted with water and extracted with DCM. The combined organic layers are dried over MgSC^, concentrated in vacuo and the product purified by RP HPLC. Yield: 1.73 g (75%). HPLC-MS: M+H=424; tR=1.59 min (*Method_5).
75%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In dimethyl sulfoxide; at 65℃; for 39h;Inert atmosphere;	General procedure: D2a) [6-[2-[methyl-[(2-methylpropan-2-yl)oxycarbonyl]amino]propanoylamino]-2-(2-phenylethynyl)pyridin-3-yl]boronic acid A mixture of tert-butyl-N-[1-[[5-bromo-6-(2-phenylethynyl)pyridin-2-yl]amino]-1-oxo-propan-2-yl]-N-methylcarbamate C2a (2.5 g, 5.45 mmol), bis(neopentyl glycolato)diboron (2.46 g, 10.9 mmol), KOAc (1.61 g, 16.4 mmol), 1,1'-Bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (399 mg, 0.55 mmol) and DMSO (20 ml) is stirred under argon atmosphere for 39 h at 65 C. The mixture is diluted with water and extracted with DCM. The combined organic layers are dried over MgSO4, concentrated in vacuo and the product purified by RP HPLC. Yield: 1.73 g (75%). HPLC-MS: M+H=424; tR=1.59 min (*Method-5).

Reference： [1]Patent: WO2013/127729,2013,A1 .Location in patent: Page/Page column 57; 58
[2]Patent: US2013/225567,2013,A1 .Location in patent: Paragraph 0280; 0281

61
[ 19936-14-2 ]
[ 201733-56-4 ]
[ 1467059-89-7 ]

Yield	Reaction Conditions	Operation in experiment
76%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 110℃; for 2h;Inert atmosphere;	A mixture of 5,5,5',5'-tetramethyl-2,2'-bi(1,3,2-dioxaborinane) (16.50 g, 48.33 mmol), oven dried potassium acetate (20.03 g, 204.1 mmol), and <strong>[19936-14-2]1-(4-bromophenyl)cyclobutanol</strong> (10.00 g, 44.03 mmol) in 1,4-dioxane (120 mL) was degassed with N2 for 15 min, then treated with [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (2.44 g, 2.99 mmol). The reaction mixture was heated to 110 C. and stirred for 2 hours under N2. The reaction mixture was cooled to room temperature and filtered through celite, eluting with EtOAc. The filtrate was evaporated to give a black oil, which was purified by flash chromatography (0-50% EtOAc/Heptane) three times to afford the title compound (8.68 g, 76%) as a white solid. GC/MS: 259. 1H NMR (400 MHz, CD3Cl) delta 7.83 (d, J=8.05 Hz, 2H), 7.50 (d, J=8.29 Hz, 2H), 3.78 (s, 4H), 2.65-2.52 (m, 2H), 2.38-2.42 (m, 2H), 1.98-2.03 (m, 1H), 1.72-1.80 (m, 1H), 1.03 (s, 6H).

Reference： [1]Organic Process Research and Development,2018,vol. 22,p. 681 - 696
[2]Patent: US2013/267493,2013,A1 .Location in patent: Paragraph 0698; 0712; 1153
[3]Journal of Medicinal Chemistry,2018,vol. 61,p. 2372 - 2383

62
[ 201733-56-4 ]
[ 836-59-9 ]
[ 1467060-34-9 ]

Yield	Reaction Conditions	Operation in experiment
34%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 110℃; for 1h;Inert atmosphere; Microwave irradiation;	To a solution of <strong>[836-59-9]4-[2-(4-bromophenoxy)ethyl]morpholine</strong> (498 mg, 1.74 mmol) in 1,4-dioxane (10 mL) was added 5,5,5',5'-tetramethyl-2,2'-bi(1,3,2-dioxaborinane) (431 mg, 1.91 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (124 mg, 0.174 mmol) and KOAc (0.853 g, 8.7 mmol). The mixture was degassed with nitrogen for 3 min and heated to 110 C. by microwave irradiation for 1 h. The mixture was concentrated in vacuo to give a residue, which was dissolved with ethyl acetate (50 mL) and washed with brine (2*15 mL). The organic layer was dried over Na2SO4 and concentrated in vacuo to give a residue, which was purified by flash chromatography to give 4-{2-[4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenoxy]ethyl}morpholine (190 mg, 34%) as a colorless oil.

Reference： [1]Patent: US2013/267493,2013,A1 .Location in patent: Paragraph 0805

63
[ 98480-31-0 ]
[ 201733-56-4 ]
[ 1467060-42-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In tetrahydrofuran; at 20 - 70℃; for 3h;Inert atmosphere;	To a solution of [1-(4-bromophenyl)cyclopropyl]methanol (1200 mg, 5.3 mmol) in THF (40 mL) was added 5,5,5',5'-tetramethyl-2,2'-bi-1,3,2-dioxaborinane (1600 mg, 6.87 mmol), KOAc (2600 mg, 26.5 mmol) and Pd(dppf)Cl2 (197 mg, 0.27 mmol) at room temperature under N2. The reaction mixture was stirred at 70 C. under N2 for 3 hours. The reaction was filtered, the filtrate was concentrated, and purified by column chromatography to give the title compound (1.3 g, 95%) as a white solid. 1H NMR (400 MHz, CDCl3) delta 7.74 (d, 2H), 7.34 (d, 2H), 3.75 (s, 4H), 3.68 (s, 2H), 0.99 (s, 6H), 0.88 (m, 2H), 0.85 (m, 2H).

Reference： [1]Patent: US2013/267493,2013,A1 .Location in patent: Paragraph 0822

64
[ 122531-09-3 ]
[ 201733-56-4 ]
[ 1467061-15-9 ]

Yield	Reaction Conditions	Operation in experiment
55%	With potassium acetate; In dimethyl sulfoxide; at 100℃; for 1h;	To a solution of <strong>[122531-09-3]5-bromo-6-chloro-1H-indole</strong> (5.0 g, 22 mmol) in DMSO (30 mL) was added 5,5,5',5'-tetramethyl-2,2'-bi-1,3,2-dioxaborinane (6.4 g, 28 mmol) and KOAc (10.3 g, 0.11 mol). The sealed vial was heated to 100 C. for 1 h. The reaction was quenched with water (100 mL) mL) and extracted with ethyl acetate. The combined organics were dried and concentrated in vacuo to give the title compound (2.9 g, 55% yield) as a yellow solid. 1H NMR (400 MHz, CDCl3) delta 8.11 (br. s., 1H), 7.99 (s, 1H), 7.37 (s, 1H), 7.14 (s, 1H), 6.51 (s, 1H), 3.83 (s, 4H), 1.08 (s, 6H).

Reference： [1]Patent: US2013/267493,2013,A1 .Location in patent: Paragraph 1028; 1029

65
[ 25109-28-8 ]
[ 201733-56-4 ]
C₁₇H₂₅BO₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 115℃; for 1h;Inert atmosphere; Microwave irradiation;	A mixture of 5,5,5',5'-tetramethyl-2,2'-bi-1,3,2-dioxaborinane (75.0 mg, 0.22 mmol), oven dried potassium acetate (94.1 mg, 0.95 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (19.0 mg, 0.023 mmol), and <strong>[25109-28-8]1-bromo-4-cyclohexylbenzene</strong> (49.5 mg, 0.21 mmol) in 1,4-dioxane (2 mL) was degassed with N2 for 10 minutes, and subjected to microwave irradiation at 115 C. for one hour. The black reaction mixture was cooled, filtered through cotton, and concentrated in vacuo to give a dark solid. To the dark solid was added 5-bromo-6-chloro-1H-indazole-3-carboxylic acid (55.6 mg, 0.20 mmol), 2 N aqueous potassium carbonate solution (0.40 mL, 0.81 mmol) and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane adduct (16.3 mg, 0.020 mmol). The reaction mixture was diluted with degassed toluene (1 mL) and EtOH (1 mL), and heated at 110 C. for 18 hours in a sealed reaction vessel. The cooled reaction mixture was concentrated in vacuo and partitioned between 2 N citric acid (15 mL) and EtOAc (15 mL). The layers were separated, and the aqueous phase was extracted with EtOAc (15 mL). The combined organic layers were dried over Na2SO4 and concentrated in vacuo to give a dark oil, which was purified by reverse phase HPLC (Column: Waters XBridge C18 19100 mm, 5 mum; Mobile phase A: 0.03% NH4OH in water (v/v); Mobile phase B: 0.03% NH4OH in MeCN (v/v); 80.0% H2O/20.0% MeCN linear to 40% H2O/60% MeCN in 8.5 min, 40% H2O/60% MeCN linear to 0% H2O/100% MeCN in 0.5 min, HOLD at 0% H2O/100% MeCN to 10.0 min. Flow: 25 mL/min) to give the title compound (6.2 mg, 9% yield). MS (ES+) 355.1 (M+H)+. Retention time=3.65 minutes (Column: Waters Atlantis dC18 4.650 mm, 5 mum; Mobile phase A: 0.05% TFA in water (v/v); Mobile phase B: 0.05% TFA in MeCN (v/v); Gradient: 95:5 A:B linear to 5:95 A:B in 4.0 min, hold at 5:95 A:B to 5.0 min. Flow: 2 mL/min).

Reference： [1]Patent: US2013/267493,2013,A1 .Location in patent: Paragraph 1171

66
[ 151583-29-8 ]
[ 201733-56-4 ]
[ 833472-82-5 ]

Yield	Reaction Conditions	Operation in experiment
64%	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; dimethyl sulfoxide; at 90℃;Inert atmosphere; Sealed tube;	Example 37B: 3-(3-methoxy-3-oxopropyl)phenylboronic acid j00413j DMSO (6.86 mL) and dioxane (6.86 mL) were degassed for 15 mm bybubbling with argon. Meanwhile, Example 37A (400 mg, 1.645 mmol), KOAc (404 mg,4.11 mmol), and bis(neopentyl glycolato)diboron (520 mg, 2.304 mmol) were placed in amicrowave tube. To these compounds was added the degassed solvents. The tube was sealed and degassed for an additional 15 mi [1,1?-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (135 mg, 0.165 mmol) was subsequently added, the tubesealed, and heated to 90 C and allowed to stir overnight. The reaction was diluted withEtOAc and washed twice with brine, dried (Na2SO4), filtered, and concentrated in vacuo.The crude reaction mixture was purified by Prep LC (Axia Luna 5 t Cl 8 3 Ox 100 mmcolumn, 10 mm gradient from 40 to 100% B in A, A = 10:90:0.1 MeCN:H20:TFA, B =90:10:0.1 MeCN:H20:TFA) to yield Example 37B (O.224g, 64%) which was usedimmediately after purification.

Reference： [1]Patent: WO2014/201073,2014,A1 .Location in patent: Paragraph 00413

67
[ 2296-23-3 ]
[ 201733-56-4 ]
3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-4-hydroxybenzonitrile [ No CAS ]

Reference： [1]Advanced Synthesis and Catalysis,2015,vol. 357,p. 2287 - 2300

68
[ 2296-23-3 ]
[ 201733-56-4 ]
4-cyano-2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyltrifluoromethanesulfonate [ No CAS ]

Reference： [1]Advanced Synthesis and Catalysis,2015,vol. 357,p. 2287 - 2300

69
[ 207115-22-8 ]
[ 201733-56-4 ]
4-bromo-2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenol [ No CAS ]

Reference： [1]Advanced Synthesis and Catalysis,2015,vol. 357,p. 2287 - 2300

70
[ 207115-22-8 ]
[ 201733-56-4 ]
4-bromo-2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)phenyltrifluoromethanesulfonate [ No CAS ]

Reference： [1]Advanced Synthesis and Catalysis,2015,vol. 357,p. 2287 - 2300

71
[ 1810-66-8 ]
[ 201733-56-4 ]
C₉H₈BNO₃ [ No CAS ]

Reference： [1]ACS Medicinal Chemistry Letters,2015,vol. 6,p. 590 - 595

72
[ 82019-32-7 ]
[ 201733-56-4 ]
7-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1-methylquinoxalin-2(1H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
30%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 80.0℃; for 3.0h;Inert atmosphere;	Bis(neopentyl glycolato)diboron (1.42 mg, 6.30 mmol) and potassium acetate (823 mg, 8.40 mmol) were added to a solution of <strong>[82019-32-7]7-bromo-1-methylquinoxalin-2(1H)-one</strong> (1.0 g, 4.2 mmol) in 1,4-dioxane (15 mL). The reaction mixture was degassed under nitrogen for 30 min before Pd(dppf)Cl2.DCM (171 mg, 0.21 mmol) was added. The reaction mixture was heated at 80 C. for 3 h. After this time the reaction mixture was concentrated under reduced pressure and purified by silica gel column chromatography eluting with 30% EtOAc in iso-hexane to afford an orange solid. Trituration with diethyl ether afforded the title compound as an off-white solid (340 mg, 30%). 1H NMR (400 MHz, CDCl3): delta 8.37-8.30 (m, 1H), 7.79 (m, 3H), 3.82 (s, 4H), 3.75 (s, 3H), 1.06 (s, 6H).
30%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 80.0℃; for 3.0h;Inert atmosphere;	Bis(neopentyl glycolato)diboron (1.42 mg, 6.30 mmol) and potassium acetate (823 mg, 8.40 mmol) were added to a solution of <strong>[82019-32-7]7-bromo-1-methylquinoxalin-2(1H)-one</strong> (1.0 g, 4.2 mmol) in 1,4-dioxane (15 mL). The reaction mixture was degassed under nitrogen for 30 min before Pd(dppf)Cl2.DCM (171 mg, 0.21 mmol) was added. The reaction mixture was heated at 80 C. for 3 h. After this time the reaction mixture was concentrated under reduced pressure and purified by silica gel column chromatography eluting with 30% EtOAc in iso-hexane to afford an orange solid. Trituration with diethyl ether afforded the title compound as an off-white solid (340 mg, 30%).

Reference： [1]Patent: US2015/210655,2015,A1 .Location in patent: Paragraph 0253
[2]Patent: US9522894,2016,B2 .Location in patent: Page/Page column 28

73
[ 55580-07-9 ]
[ 201733-56-4 ]
C₁₄H₁₉BO₅ [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2015,vol. 58,p. 6225 - 6236

74
[ 29421-92-9 ]
[ 201733-56-4 ]
5,5-dimethyl-2-(5-methyl-3-thienyl)-1,3,2-dioxaborinane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 120℃;Inert atmosphere;	531 rng <strong>[29421-92-9]4-bromo-2-methyl-thiophene</strong> (3.0 mmol), 813 mg 2-(5,5-dimethyl-l,3,2- dioxaborinan-2-yl)-5,5-dimethyl-1,3,2-dioxaborinane (3.6 mmol) and 883 mg KOAc (9.0rnrnol) were dissolved in 15 mL 1,4-dioxane, then 219 mg Pd(dppf)C12 (0.3 mmol) was added. The mixture was heated under nitrogen at 120C in a microwave reactor until no further conversion was observed. The volatiles were evaporated under reduced pressure and purified via flash chromatography using heptane and ethyl acetate as eluents to obtain 5,5-dimethyl-2-(5-methyl-3 -thienyl)- 1,3 ,2-dioxaborinane. ?H NMR (500 MHz, CDCI3):7.59 (d, TH), 7.00 (dd, lH), 3.73 (s, 411), 2.49 (d, 3H), 1.02 (s, 611).

Reference： [1]Patent: WO2015/97123,2015,A1 .Location in patent: Page/Page column 385

75
[ 201733-56-4 ]
[ 166953-64-6 ]
benzyl 4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)piperidine-1-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With triphenylphosphine; copper(I) bromide; lithium tert-butoxide; In N,N-dimethyl acetamide; at 25℃; for 18h;Inert atmosphere; Schlenk technique;	General procedure: In air, CuBr (7.1 mg, 0.05 mmol), PPh3 (17.03 mg, 0.065 mmol), LiOtBu(80 mg, 1mmol), and bis(neopentyl glycolato) diboron (168mg, 0.75 mmol ) were added to aSchlenk tube equipped with a stir bar. The vessel was evacuated and filled with argon(three cycles). DMAc (1 mL), alkyl halide (0.5 mmol) were added in turn by syringeunder an argon atmosphere (if the alkyl halide is a solid, it was added along with theCuBr). The resulting reaction mixture was stirred vigorously at 25 C for 18 h. Thereaction mixture was then diluted with EtOAc, filtered through silica gel with copiouswashings (petroleum ether to EtOAc), concentrated, and purified by columnchromatography.

Reference： [1]Chemistry Letters,2016,vol. 45,p. 200 - 202

76
[ 1753-75-9 ]
[ 201733-56-4 ]
5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzo[c][1,2,5]thiadiazole [ No CAS ]

Reference： [1]Organometallics,2016,vol. 35,p. 1008 - 1014

77
[ 1357293-53-8 ]
[ 201733-56-4 ]
[ 346656-39-1 ]

Reference： [1]Advanced Synthesis and Catalysis,2016,vol. 358,p. 2417 - 2421

78
2-(1-(naphthalen-1-yl)ethoxy)pyridine [ No CAS ]
[ 201733-56-4 ]
[ 1127-76-0 ]
5,5-dimethyl-2-(1-(naphthalen-1-yl)ethyl)-1,3,2-dioxaborinane [ No CAS ]

Reference： [1]Advanced Synthesis and Catalysis,2016,vol. 358,p. 2417 - 2421

79
[ 1375108-41-0 ]
[ 201733-56-4 ]
(3-methylquinolin-7-yl)boronic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 20 - 90℃;Inert atmosphere;	A solution of 7-bromo-3 -methylquinoline (258 mg, 1.16 mmol), 5,5,5?, 5?-tetramethyl-2,2?-bi( 1,3 ,2-dioxaborinane) (656mg, 2.90 mmol), PdC12(dppf)*dcm (47.4 mg, 0.058 1 mmol), and KOAc (342 mg, 3.49 mmol) in dioxane (5809 tL, 1.16 mmol) was sparged with N2(g) for 5 mm at ambient temperature and then heated at 90 C overnight. After cooling to ambient temperature, the reaction mixture was partitioned between EtOAc and water. The combined organic extracts were washed with brine, dried over anhydrous Na2SO4(), filtered and concentrated under vacuum to afford the title compound with higher than expected mass, but assumed with quantitative yield (217 mg, 100% yield). MS (apci) m/z = 188.1 (M+H).

Reference： [1]Patent: WO2017/70708,2017,A1 .Location in patent: Paragraph 00586

80
[ 92-53-5 ]
[ 201733-56-4 ]
[ 5123-13-7 ]

Reference： [1]Organic Letters,2018,vol. 20,p. 1995 - 1998

81
[ 52092-47-4 ]
[ 201733-56-4 ]
C₁₀H₁₅BN₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%		Under nitrogen protection, 550 mL of dioxane and <strong>[52092-47-4]2-nitro-5-chloropyridine</strong> (15.8 g, were added to the reaction flask in turn. 0.10 mol), neopentyl glycol diborate (22.6 g, 0.10 mol), potassium acetate (14.7 g, 0.15 mol), after stirring uniformly, finally adding catalyst PdCl2dppf (0.74 g, 0.001 mol), slowly heating to 80 -90 ° C, Stir the reaction for 2-3 h. After the end of the GC reaction, the reaction was stopped by cooling, and the reaction solution was filtered through celite to obtain a dark-black reaction solution. After charging at 3 atm of hydrogen, the reaction was carried out at room temperature overnight. After the reaction was completed, the activated carbon was decolorized, and the filtrate was distilled under reduced pressure until no liquid was poured. / heptane mixed solvent was cooled and beaten for half an hour, filtered to obtain an off-white product, heated again with ethanol, and then cooled down, and the filter cake was rinsed with -20 ° C anhydrous ethanol, and dried to obtain an off-white solid 14.0 g. 68percent, HPLC purity 98.9percent

Reference： [1]Patent: CN108047258,2018,A .Location in patent: Paragraph 0005; 0024; 0025

82
[ 22353-33-9 ]
[ 201733-56-4 ]
C₁₀H₁₅BN₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
74%		Under nitrogen protection, 750 mL of toluene and <strong>[22353-33-9]3-nitro-5-chloropyridine</strong> (15.8 g, were sequentially added to the reaction flask. 0.10 mol), neopentyl glycol diborate (22.6 g, 0.10 mol), potassium acetate (24.5 g, 0.25 mol), after stirring uniformly, finally adding catalyst PdCl2dppf (0.74 g, 0.001 mol), slowly heating to 100 -105 C, The reaction was stirred for 8-10 h. After the completion of the GC reaction, the reaction was stopped by cooling, and the reaction solution was filtered through celite to obtain a dark-black reaction solution. After adding 100 mL of ethanol, the mixture was charged with 3 atm of hydrogen and allowed to react at room temperature overnight. After the reaction was completed, the activated carbon was decolorized, and the filtrate was distilled under reduced pressure until The liquid solution was added to an ethanol/heptane mixed solvent to cool and beat for half an hour, and filtered to obtain a light gray product. After again using ethanol solubility, the temperature was precipitated, and the filter cake was rinsed with -20 C anhydrous ethanol, and dried to obtain a pale yellow solid. 15.2g, yield 74%, HPLC purity 98.1%

Reference： [1]Patent: CN108047258,2018,A .Location in patent: Paragraph 0005; 0026; 0027

83
[ 928-49-4 ]
[ 140681-55-6 ]
[ 201733-56-4 ]
(E)-2-(4-fluorohex-3-en-3-yl)boronic acid neopentylglycol ester [ No CAS ]

Reference： [1]Organic Letters,2018,vol. 20,p. 5242 - 5246

84
[ 52287-51-1 ]
[ 201733-56-4 ]
2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-5,5-dimethyl-1,3,2-dioxaborinane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With palladium bis[bis(diphenylphosphino)ferrocene] dichloride; potassium acetate; In dimethyl sulfoxide; at 90℃; for 0.25h;	(1) Dissolving 0.01 mol of <strong>[52287-51-1]6-bromo-1,4-benzodioxane</strong> in 5 mL of DMSO,A solution was obtained, and 0.016 mol of bis(neopentyl glycol) diboron was dissolved in 4 mL of DMSO.Obtaining B solution, 0.005 mol of PbCl2 (dppf) and0.02 mol of potassium acetate is immobilized on the continuous flow reactor channel,Continuous addition of solution A and solution B at 90 CAfter 15 min, the reaction was terminated after exiting the reaction tube to obtain an intermediate;

Reference： [1]Patent: CN108440588,2018,A .Location in patent: Paragraph 0050; 0052; 0053; 0068-0079

85
[ 36953-37-4 ]
[ 201733-56-4 ]
4-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)pyridin-2(1H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 90℃; for 24h;Inert atmosphere;	To 4-bromopyridin-2(lH)-one (0.90 g, 5.2 mmol) in dioxane (lOmL) was added 5,5,5',5'-tetramethyl-2,2'-bi(l,3,2-dioxaborinane) (1.3 g, 5.7 mmol), potassium acetate (1.5 g, 16 mmol). The reaction mixture was degassed with N2 for 15 min. and (0656) PdC12(dppf)DCM was added (0.21 g, 0.26 mmol) and the reaction mixture was heated to 90 C for 24 h. The reaction mixture was partitioned with water (20 mL) and ethyl acetate (50 mL). The aqueous layer was extracted with ethyl acetate (2 x 20 mL). The combined organic layers were washed with brine (15 mL) and dried (MgS04), filtered and concentrated under reduced pressure to afford4-(5,5-dimethyl-l,3,2-dioxaborinan-2- yl)pyridin-2(lH)-one as a dark oil LCMS m/z = 208 (M+H).+

Reference： [1]Patent: WO2019/14300,2019,A1 .Location in patent: Page/Page column 72

86
[ 81971-39-3 ]
[ 201733-56-4 ]
5-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)-1-methylpyridin-2(1H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; In 1,4-dioxane; at 90℃; for 18h;Inert atmosphere;	To 5-bromo-l-methylpyridin-2(lH)-one (0.75 g, 3.9 mmol) in dioxane was added 5,5,5',5'-tetramethyl-2,2'-bi(l,3,2-dioxaborinane) (1.0 g, 4.4 mmol), KOAc (1.2 g, 12 mmol). The reaction mixture was degassed with N2, then PdCl2(dppf)-DCM (0.16 g, 0.19mmol) was added and the reaction mixture was heated to 90 C for 18 h. The reaction mixture was allowed to cool, filtered and partitioned with water (20 mL) and EtOAc (50 mL). The aqueous layer was extracted with EtOAc (2 x 20 mL). The combined organic layers were washed with brine (15 mL) and dried (MgS04), filtered and concentrated under reduced pressure to afford 5-(5,5-dimethyl-l,3,2-dioxaborinan-2-yl)-l- methylpyridin-2(lH)-one (0.67 g, 76 % yield) as a dark oil). LCMS m/z = 222 (M+H).+

Reference： [1]Patent: WO2019/14300,2019,A1 .Location in patent: Page/Page column 74

87
[ 159503-91-0 ]
[ 201733-56-4 ]
[ 1167991-21-0 ]

Yield	Reaction Conditions	Operation in experiment
72%	With copper(I) oxide; lithium methanolate; triphenylphosphine; In N,N-dimethyl-formamide; at 45 - 55℃;Inert atmosphere;	Under nitrogen protection, in the reaction bottle,<strong>[159503-91-0]N-Boc-1,2,5,6-tetrahydropyridine-4-bromo</strong> (26.3 g, 0.1 mol),Neopentyl glycol diborate (22.6 g, 0.1 mol),Cuprous oxide (1.43 g, 0.01 mol), triphenylphosphine (5.24 g, 0.02 mol),Lithium methoxide (7.2 g, 0.2 mol) was dissolved in N,N-dimethylformamide (130 g).The temperature is controlled from 45 C to 55 C to stir the reaction;After the GC reaction is completed, the reaction mixture is filtered through a pad of diatomaceous earth.The filter cake was rinsed with toluene (50 g) and the filtrate was diluted with toluene (50 g).The filtrate was washed with water (100 g) and layered.The organic layer was detected by GC without N,N-dimethylformamide.The organic layer was washed with saturated brine (100 g) and evaporated to dryness.Add heptane / ethanol = 5:1 beating,After filtration, 21.2 g of white solid N-Boc-1,2,5,6-tetrahydropyridine-4-boronic acid neopentyl glycol ester was obtained, HPLC: 99.8%, yield 72%.

Reference： [1]Patent: CN109762007,2019,A .Location in patent: Paragraph 0021

88
[ 42872-73-1 ]
[ 201733-56-4 ]
[ 1448644-58-3 ]

Yield	Reaction Conditions	Operation in experiment
84%		A mixture of <strong>[42872-73-1]2-bromo-4-methylbenzonitrile</strong> (2.00 g, 10.2 mmol), 5, 5, 5', 5'- tetramethyl-2,2'-bi(l,3,2-dioxaborinane) (3.06 g, 13.6 mmol) and potassium acetate (3.00 g, 30.6 mmol) in anhydrous DMSO (10 mL), in a sealable flask, was purged with Argon for 20 min before PdChldppfj-Cl ECl? adduct (0.25 g, 0.34 mmol) was added, the flask was sealed and the reaction heated at 80 C. After 17 hrs, the reaction was cooled to RT before being partitioned between EtOAc and brine. The layers were separated and the aqueous layer was extracted once more with EtOAc. The organic layers were combined, washed with brine, dried (MgS04), filtered and concentrated in vacuo to afford a brown oil which solidified upon standing. Purification by Isco chromatography afforded 301 A as an off-white solid (1.96 g; 84% yield). NMR (400MHz, DMSO-d6) d 7.72 - 7.63 (m, 2H), 7.43 (dd, 7=7.9, 1.1 Hz, 1H), 3.79 (s, 4H), 2.38 (s, 3H), 0.98 (s, 6H).

Reference： [1]Patent: WO2020/23355,2020,A1 .Location in patent: Page/Page column 39; 204-205

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[ CAS No. 201733-56-4 ] {[proInfo.proName]}

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[ 201733-56-4 ] Synthesis Path-Upstream 1~8

[ 201733-56-4 ] Synthesis Path-Downstream 1~88

Pharmaceutical Intermediates of [ 201733-56-4 ]

Bortezomib Related Intermediates

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Organoboron

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Other Aliphatic Heterocycles

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[ 201733-56-4 ]

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[ 201733-56-4 ]