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Chemical Structure| 199609-62-6 Chemical Structure| 199609-62-6

Structure of 199609-62-6

Chemical Structure| 199609-62-6

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Product Details of [ 199609-62-6 ]

CAS No. :199609-62-6
Formula : C12H18BNO4
M.W : 251.09
SMILES Code : CC(C)(C)OC(=O)NCC1=CC=CC(=C1)B(O)O
MDL No. :MFCD06246052
InChI Key :YHAQUGOSDQZIMA-UHFFFAOYSA-N
Pubchem ID :3684686

Safety of [ 199609-62-6 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H317
Precautionary Statements:P261-P280

Application In Synthesis of [ 199609-62-6 ]

* 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.

  • Downstream synthetic route of [ 199609-62-6 ]

[ 199609-62-6 ] Synthesis Path-Downstream   1~35

  • 1
  • [ 199609-45-5 ]
  • [ 199609-62-6 ]
  • [3-(4,5,6-Trimethoxy-7-oxo-cyclohepta-1,3,5-trienyl)-benzyl]-carbamic acid tert-butyl ester [ No CAS ]
  • 2
  • [ 52415-29-9 ]
  • [ 199609-62-6 ]
  • [3-(1H-Indol-6-yl)-benzyl]-carbamic acid tert-butyl ester [ No CAS ]
  • 3
  • [ 10075-50-0 ]
  • [ 199609-62-6 ]
  • [3-(1H-Indol-5-yl)-benzyl]-carbamic acid tert-butyl ester [ No CAS ]
  • 4
  • [ 199609-62-6 ]
  • [ 210889-34-2 ]
  • 3-{7-[3-(tert-Butoxycarbonylamino-methyl)-phenyl]-1H-indol-3-yl}-propionic acid ethyl ester [ No CAS ]
  • 5
  • [ 199609-62-6 ]
  • [ 210889-33-1 ]
  • 3-{6-[3-(tert-Butoxycarbonylamino-methyl)-phenyl]-1H-indol-3-yl}-propionic acid ethyl ester [ No CAS ]
  • 6
  • [ 909036-40-4 ]
  • [ 199609-62-6 ]
  • [ 909036-41-5 ]
  • 7
  • [ 1003933-74-1 ]
  • [ 199609-62-6 ]
  • [ 1003933-78-5 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In water; N,N-dimethyl-formamide; at 100℃; for 0.5h;microwave irradiation; EXAMPLE 227; 5-[3'-(aminomethyI)biphenyl-3-yl]-l,4-dihydroxy-l,8-naphthyridin-2-(l H)-one; Step 1 : ter/-butyl ({3'-[8-benzyloxy)-5-hydroxy-7-oxo-7,8-dihydro-l ,8-naphthyridin-4- yl]biphenyl-3-yl}methyl) carbamate; The Ethyl l-(benzyloxy)-5-( 3-bromophenyl)-4-hyroxy-2-oxo-l,2-dihydro-l,8- naphthyridine-3-carboxylate (Example 225, Step 4, 0.100 g3 0.202 mmol) was dissolved in DMF (5.0 mL) and H2O (1.0 mL). To this was added 3-(N-BOC-aminomethyl)phenylboronic acid (0.101 g, 0.404 mmol), potassium carbonate (0.084 g, 0.606 mmol), and the Pd dppf (DCM adduct) catalyst (0.008 g, 0.010 mmol) while N2 was bubbled through the solution. The reaction vessel was sealed and the reaction heated in a microwave at 1000C for 0.5 hour. The solution was cooled to room temperature, diluted with H2O ( 6 mL), and extracted into EtOAc (3x 10 mL). The organic layers were combined, dried, filtered, and concentrated. The residue was purified by SGC (0-50% EtOAc/hexane) to afford the title compound. ES MS: m/z = 622 (M +
  • 8
  • [ 1003933-82-1 ]
  • [ 199609-62-6 ]
  • [ 1003933-86-5 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In water; N,N-dimethyl-formamide; at 100℃; for 0.166667h;microwave irradiation; Step 2: tert-butyl [(3'-[l-(benzyloxy)-2-oxo-l,2-dihyrdo-l,8-naphmvridm-4- yl]methyl}biphenyl-3-yl)methyl]carbamate; The l-(benzyloxy)-4-(3-bromobenzyl)-l,8-naphthyridin-2(l H)-one (0.150 g, 0.356 mmol) was dissolved in DMF (5.0 mLs) and H2O (1.0 mL). To this was added 3-(N-BOC- aminomethyl)phenylboronic acid (0.179 g, 0.712 mmol), potassium carbonate (0.148 g, 1.068 mmol), and the Pd dppf (DCM adduct) catalyst (0.015 g, 0.018 mmol) while N2 was bubbled through the solution. The reaction vessel was sealed and the reaction heated in a microwave at 100 0C for 10 minutes. The solution was cooled to room temperature, diluted with aqueous HCl (IN, 6 mL), and extracted into EtOAc (10 mL). The organic layer was dried, filtered, and concentrated. ES MS: m/z - 548 (M + 1).
  • 9
  • [ 1003934-37-9 ]
  • [ 199609-62-6 ]
  • [ 1003934-41-5 ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In water; N,N-dimethyl-formamide; at 100℃; for 0.5h;microwave irradiation; Step 2: ethyl 1 -(benzyloxy)-5-[(3'-[(tert-butoxycarbonyl)amino]methyl}biphenyl-3- yl)methyl]-4-hydroxy-2-oxo-l ,2-dihydro-l, S-naphthyridine-S-carboxylate.; Ethyl l-(benzyloxy)-5-(3-bromoben2yl)-4-hydroxy-2-oxo-l,2-dihydro-l,8- naphthyridine-3-carboxylate: from step 1 (0.200 g, 0.41 mmol) was dissolved in DMF (5.0 mL) and H2O (1.0 mL). To this was added 3-(N-BOC-aminomethyl)phenylboronic acid (0.101 g, 0.404 mmol), K2CO3 (0.084 g, 0.606 mmol), and the Pd dppf (DCM adduct) catalyst (0.008 g,0.010 mmol) while N2 was bubbled through the solution. The reaction vessel was sealed and the reaction heated in a microwave at 1000C for 0.5 hour. The solution was cooled to room temperature, diluted with H2O (6 mL), and extracted into EtOAc (3x 10 mL). The organic layers were combined, dried, filtered, and concentrated. The residue was purified by SGC (0-100% EtOAc/hexane) to afford the title compound (150 mgs). ES MS: m/z = 636.1 (M + 1).
  • 10
  • [3-(aminomethyl)phenyl]boronic acid [ No CAS ]
  • [ 199609-62-6 ]
YieldReaction ConditionsOperation in experiment
For compounds (2-6) the commercially available 4-aminomethylphenylboronic acid and 3-aminomethylphenylboronic acid were BOC protected under standard conditions (Wei et al., 2000) and the appropriate boronic acid was used at the Suzuki coupling stage in the synthesis of compounds (2-6). The BOC group was removed with 4 M HCl in dioxane at RT after hydrazone coupling;
  • 11
  • [ 905735-46-8 ]
  • [ 199609-62-6 ]
  • [ 905735-59-3 ]
YieldReaction ConditionsOperation in experiment
83% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In erthanol; water; toluene; at 95℃; for 0.5h; Example A9; 7-[3-(aminomethyl)phenyl]-1-methyl-1H-imidazo[4,5-d]thieno[3,2-b]pyridin-4-amine trifluoroacetate salt; A9.1: 4-Chloro-7-[3-(t-butyloxycarbonylaminomethyl)phenyl]-1-methyl-1H-imidazo[4,5-d]thieno[3,2-b]pyridine; A mixture of A2.8 (620 mg; 2.05 mmol), 3-(N-Bocaminomethyl)phenylboronic acid, [purchased from Frontier Scientific] (652 mg; 2.60 mmol), tetrakis(triphenylphosphine)palladium(0) (60 mg; 0.048 mmol), 2M Na2CO3 (4 ml), ethanol (5 ml) and toluene (8 ml) was vigorously stirred at 95 C. for 0.5 hr. After cooling to rt, the reaction mixture was partitioned between ethyl acetate (100 ml) and water (25 ml). After drying (MgSO4), the organic layer was concentrated to afford a yellow oil, that was chromatographed on a 5×15 cm silica gel column using a stepwise gradient from 100% dichloromethane to 3% methanol in dichloromethane. The purest fractions were concentrated to afford 729 mg (83%) of A9.1 as a light yellow foam. 1H-NMR (CDCl3) δ: 7.97 (1H, s), 7.82 (1H, s), 7.63 (2H, m), 7.44 (2H, t, J=7.5 Hz), 7.33 (1H, d, J=7.5 Hz), 4.95 (1H, m), 4.40 (2H, d, J=5.5 Hz), 4.16 (3H, s), 1.48 (9H, s) HPLC (A): 99%, ret. time 1.86 min., LC/MS (M+H)+=429.12 (431.12).
  • 12
  • [ 887147-33-3 ]
  • [ 199609-62-6 ]
  • [[3-[8-methyl-5-(methylamino)-8H-imidazo[4,5-d]thiazolo[4,5-b]pyridin-2-yl]phenyl]methyl]carbamic acid 1,1-dimethylethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,4-dioxane; ethanol; water; at 100℃; for 0.833333h; Example A44; rr3-r8-methyl-5-(methylamino')-8H-imidazor4.5-dlthiazolo[4,5-b]pyridin-2- yllphenyllmethyll carbamic acid 1,1 -dimethyl ethyl ester; A44A3.3 (25 mg, 0.084 mmol), 3-(t-butyloxycarbonylaminomethyl)phenylboronic acid (21 mg, 0.085 mmol) and tetrakis(triphenylphosphine)palladium (0) (9.7mg, 0.008 mmol) was added to a mixture of 2M aqueous sodium carbonate (0.18 mL) dioxane83 EPO <DP n="85"/>(0.40 mL) and ethanol (0.40 mL). The reaction mixture was heated under argon for 50 minutes at 100 0C. The reaction mixture allowed to cool to room temperature and the solvents were removed under reduced pressure. Water (6 mL) was added and placed in an ice bath. The precipitate was collected by filtration, washed with additional water and dried under vacuum. The solid was rinsed with hexane to yield 38.8 mg of a tan solid. The crude product was purified by flash silica gel column chromatography (98:2 ethyl acetate/methanol -^ 50:48:1:1 THF/ethyl acetate/methanol/ammonium hydroxide -> 50:45:3:2 THF/ethyl acetate/methanol/ammonium hydroxide. Fractions for which the desired mass were obtained were combined and the solvent removed under reduced pressure. The solid was suspended in hexane, filtered and rinsed with additional hexane. The solid was then triturated with a mixture of 90:10 ether/ethyl acetate to yield 10.4 mg of the desired product as a pale yellow solid. M+H+ = 425.24. 1H NMR 400 MHz ^6DMSO 5 8.24 s, IH, 8.06-7.90 m, 2H, 7.60-7.48, m, 2H, 7.40 br s, 1 H, 7.10 br s, IH, 4.24 br s, 2H, 4.06, s, 3H, 3.06, br s, 3H, 1.48 s, 9H.
  • 13
  • [ 52780-15-1 ]
  • [ 199609-62-6 ]
  • [ 943722-03-0 ]
YieldReaction ConditionsOperation in experiment
92% With sodium carbonate;tetrakis(triphenylphosphine) palladium(0); In 1,2-dimethoxyethane; water; at 120℃; for 2h; Example 16. Synthesis of N-[3'-(aminomethyl)-2-methylbiphenyl-3-yl]methyl}-5- nitro-4-(4,5,7,8-tetrahydroimidazo[4,5-d]azepin-6(lH)-yl)pyrimidin-2-amine; A solution of 3-bromo-2-methyl-benzamide (500 mg, 2.340 mmol) and pyridine (0.60 mL, 7.42 mmol) in dichloromethane (10 mL) was cooled to 0 0C and treated with trifluoroacctic anhydride (1.0 mL, 7.08 mmol). The reaction mixture was warmed to room temperature and stirred for 15 h, then partitioned between ethyl acetate (100 mL) and 1 M HCl solution (25 mL). The organic phase was washed with satd NaHCOs solution (25 mL) and brine (25 mL), dried over Na2SO4, filtered and concentrated to afford 423 mg (92%) of 3-bromo-2-methyl-benzonitrile as a pale yellow oil that was carried on without further purification.To a mixture of 3-bromo-2-mcthyl-bcnzonitrilc (400 mg, 2.04 mmol), [3-N-boc- aminomethyl)phenyl]boronic acid (768 mg, 3.06 mmol), tetrakis(triphenylphosphine)palladium (236 mg, 0.204 mmol), and sodium carbonate (649 mg, 6.12 mmol) was added dimethoxyethane (16 mL) and water (1.6 mL). The reaction mixture was sealed under N2 and heated at 120 C for 2 h. The reaction mixture was partitioned between ethyl acetate (125 mL) and 5% NaCl solution (40 mL). The organic <n="48"/>phase was washed with brine, dried over Na2SO4, filtered and concentrated. The residue was purified by silica gel chromatography eluting with 5-15% ethyl acetate in hexanes to furnish 604 mg (92%) of (3'-cyano-2'-methyl-biphenyl-3-ylmethyl)-carbamic acid tert- butyl ester, m/z 323.5 (M + H)+.A solution of (3'-cyano~2'-methyl-biphenyl-3-ylmethyl)-carbamic acid te/Y-butyl ester (100 mg, 0.31 mmol) and cobaltous chloride hexahydrate (111 mg, 0.47 mmol) in 2:1 THF/H2O (3 mL) was cooled to 0 C and treated with sodium borohydride (59 mg, 1.55 mmol), portionwise over several minutes. The reaction mixture was warmed to room temperature and stirred for 1 h. After the addition of 1 mL of cone NH4OH, the mixture was stirred for 5 min and then filtered, washing the collected solids with 2:1 THF/H2O (20 mL). The filtrates were concentrated, and the residue was partitioned between dichloromethane (15 mL) and water (5 mL). The aqueous phase was extracted with dichloromethane (2x15 mL), and the combined organic phases were washed with brine, dried over Na2SO4, filtered and concentrated to furnish 74 mg (73%) of (3'-aminomcthyl-2'-mcthyl-biphcnyl-3- yhnethyl)-carbamic acid tert-bvyl ester as an off-white solid, m/z 327.6 (M + H)+. (Osby, J. O.; Heinzman, S. W.; Ganem, B. J. Am. Chem. Soc. 1986, 108, 67-72).To a solution of (3'-aminomethyl-2'-methyl-biphenyl-3-ylmethyl)-carbamic acid tert-butyl ester (76 mg, 0.23 mmol) and diisopropylethylamine (0.045 mL, 0.26 mmol) in dichloromethane (2.0 mL) was added 2-chloro-5-nitro-4-thiocyanato-pyrimidine (50 mg, 0.23 mmol). The rxn mixture was stirred at room temperature for 72 h, then diluted with 5% MeOH in CH2Cl2 (30 mL) and washed with 1 M HCl solution (8 mL). The organic phase was washed with satd NaHCO3 solution and brine, dried over Na2SO4, filtered and concentrated. The crude product was purified by silica gel chromatography eluting with 15-30% ethyl acetate in hexanes to afford 74 mg (63%) of {2'-methyl-3'-[(5-nitro-4- thiocyanato-pyrimidin-2-ylamino)-methyl]-biphenyl-3-ylmethyl}-carbamic acid tert-buty ester, m/z 507.5 (M + H)+.To a solution of 1 ,4,5,6,7,8-hexahydro-iτnidazo[4,5-<i]azepine, di-HCl salt (37 mg, 0.18 mmol) and diisopropylethylamine (0.102 mL, 0.58 mmol) in 3:1 dichloromethane/JV,N- dimethylformamide (2.0 mL) was added {2'-methyl-3'-[(5-nitro-4-thiocyanato-pyrimidin- 2-ylamino)-methyl]-biphenyl-3-ylmethyl} -carbamic acid tert-butyl ester (74 mg, 0.15 <n="49"/>mmol). The rxn mixture was stirred at room temperature for 7.5 h, then diluted with ethyl acetate (35 mL) and washed with 5% NaCl solution (3*12 mL) and brine (15 mL), dried over Na2SO4, filtered and concentrated. The crude product was purified by silica gel chromatography eluting with 0-5% MeOH in CH2Cl2 to give 63 mg (74%) of (2'-methyl- 3'-[5-nitro-4-(4,5,7,8-tetrahydro-lH-imidazo[4,5-r|azepm-6-yl)-pyrimidin-2-ylamino]- methyl}-biphenyl-3-ylmethyl)-carbamic acid tert-butyl ester, m/z 585.8 (M + H)+.A solution of (2I-methyl-3'-[5-nitro-4-(4,5J7,8-tetrahydro-lH-imidazo[4,5-
  • 14
  • [ 805319-85-1 ]
  • [ 199609-62-6 ]
  • [ 1134816-47-9 ]
  • 15
  • [ 1191923-17-7 ]
  • [ 199609-62-6 ]
  • [ 1227193-48-7 ]
YieldReaction ConditionsOperation in experiment
With sodium carbonate;bis(di-tert-​butyl(4-​dimethylaminophenyl)​phosphine)​dichloropalladium(II); In water; N,N-dimethyl-formamide; at 100℃; for 1h;Microwave irradiation; Step 2:5-Bromo-furan-2-carboxylic acid ((S)-cyclohexyl-methylcarbamoyl-methyl)-amide (500 mg, 1.45 mmol), 2-NBoc-aminomethyl phenylboronic acid (365 mg, 1.45 mmol) and Bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium (II) salt (206 mg, 0.29 mmol) are suspended in DMF (7mL) and 2M Na2CO3 aqueous solution (2 mL) is added. The reaction is vortexed and then heated in microwave reactor at 100 0C for 60 minutes. The reaction mixture is diluted with 6 mL DMF and 4 mL of water and stirred vigorously for Ih to form a suspension that is filtered to give a light yellow solid that is used without further purification, 0.69 g, 95%, LC/MS ESI m/z (M+H)+ 470.5.
  • 16
  • [ 1222809-29-1 ]
  • [ 199609-62-6 ]
  • [ 1251951-58-2 ]
  • 17
  • [ 1251951-55-9 ]
  • [ 199609-62-6 ]
  • [ 1251951-59-3 ]
  • 18
  • [ 1251951-56-0 ]
  • [ 199609-62-6 ]
  • [ 1251951-60-6 ]
  • 19
  • [ 1251951-57-1 ]
  • [ 199609-62-6 ]
  • [ 1251951-61-7 ]
  • 20
  • [ 1258547-10-2 ]
  • [ 199609-62-6 ]
  • C33H31N3O4 [ No CAS ]
  • 21
  • [ 1266161-23-2 ]
  • [ 199609-62-6 ]
  • [ 1266161-32-3 ]
YieldReaction ConditionsOperation in experiment
83% With potassium phosphate;1,1'-bis(di-tertbutylphosphino)ferrocene; palladium diacetate; In 1,4-dioxane; at 100℃; for 2.5h;Inert atmosphere; Sealed tube; Example 73; N-(3~(3-Amino-4-(4-phenoxyphenyl)-1H-pyrazolo[3,4-c]pyridin-7-yl)benzyl)acetamideStep 1:[00198] A mixture of 2-chloro-3-fluoro-5-(4-phenoxyphenyl)isonicotinonitrile (51.7 mg, 0.159 mmol, from Step 3 of Example 59), 3-((tert- butoxycarbonylamino)methyl)phenylboronic acid (60.0 mg, 0.239 mmol), palladium(H) acetate (7.15 mg, 0.032 mmol), potassium phosphate (84 mg, 0.398 mmol) and 1,1'- bis(di-f-butylphosphino)ferrocene (15.30 mg, 0.032 mmol) was pumped and backfilled with nitrogen 3 times. Dioxane (2 mL) was added. The reaction vial was again pumped and backfilled with nitrogen 3 times, sealed and heated to 100 C for 2.5 h. The mixture was filtered through a CELITE pad and the pad rinsed with ethyl acetate (30 mL). The filtrate was concentrated. Silica gel chromatography, loading with toluene and eluting with 5-30% ethyl acetate in hexanes, gave tert-butyl 3-(4-cyano~3-fluoro-5-(4- phenoxyphenyl)pyridin-2-yl)benzycarbamate as tan solid (70.1 mg, 83% yield). .H NMR (500 MHz, CDCl3) δ ppm 8.73 (1 H, s), 7.94 (1 H, s), 7.91 (1 H5 δ5 J=7.70 Hz), 7.58 -7.65 (2 H, m), 7.36 - 7.54 (4 H, m), 7.20 (1 H, t, J=7.42 Hz)5 7.13 - 7.18 (2 H, m), 7.12 (2 H, 5, J=7.42 Hz), 4.96 (1 H, br. s), 4.34 - 4.48 (2 H5 m), 1.48 (9 H, s); MS (ES+) m/z: 440 (M+H); LC retention time: 4.718 min (analytical HPLC Method A).
  • 22
  • [ 23567-96-6 ]
  • [ 199609-62-6 ]
  • [ 1352621-58-9 ]
  • 23
  • [ 199609-62-6 ]
  • [ 1352621-63-6 ]
  • 24
  • [ 199609-62-6 ]
  • [ 1352621-54-5 ]
  • 25
  • [ 1235402-79-5 ]
  • [ 199609-62-6 ]
  • [ 1354786-27-8 ]
  • 26
  • [ 1235402-79-5 ]
  • [ 199609-62-6 ]
  • [ 1354787-13-5 ]
YieldReaction ConditionsOperation in experiment
61% With sodium carbonate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 120℃; for 0.75h;Microwave irradiation; Sealed tube; Inert atmosphere; In a 5 mL microwave vial 4-[4-bromo-2-(1-methyl-1H-pyrazol-5-yl)phenoxy]-3-cyano-N-1,3-thiazol-2-ylbenzene sulfonamide (Patent WO 2010079443, 500 mg, 0.97 mmol) was dissolved in 1,4-dioxane (3 mL) under nitrogen. (3-[(Tert-butoxycarbonyl)amino]methyl}phenyl)boronic acid (362 mg, 1.44 mmol), bis(triphenylphosphine) palladium (II) dichloride (68 mg, 0.1 mmol), sodium carbonate (204 mg, 1.92 mmol) and water (0.5 mL) were added and the reaction vessel sealed and heated to 120 C. for 45 minutes in the microwave. The reaction mixture was partitioned between ethyl acetate (20 mL) and 0.2M aqueous HCl (20 mL). The organic layer was separated, filtered then concentrated in vacuo. The residue was purified by silica gel column chromatography (ISCO, 12 g silica, 99:1 DCM:Acetic acid to 90:10:1 DCM:MeOH:Acetic acid gradient) to afford the title compound (380 mg, 61%) as a pale orange solid.1HNMR (400 MHz, CDCl3): δ 1.46 (s, 9H), 3.88 (s, 3H), 5.29 (s, 2H), 6.24 (d, 1H), 6.59 (d, 1H), 6.73 (d, 1H), 7.08 (d, 1H), 7.27 (d, 1H), 7.32 (d, 1H), 7.38 (d, 1H), 7.45 (m, 1H) 7.50 (m, 2H) 7.64 (d, 1H) 7.72 (dd, 1H), 7.90 (dd, 1H), 8.09 (d, 1H), 9.40-10.20 (br s, 2H).LCMS Rt=1.57 minutes MS m/z 643 [MH]+.
  • 27
  • [ 1355152-77-0 ]
  • [ 199609-62-6 ]
  • C38H36N4O3 [ No CAS ]
  • 28
  • [ 18813-71-3 ]
  • [ 199609-62-6 ]
  • [ 1374752-45-0 ]
YieldReaction ConditionsOperation in experiment
With potassium phosphate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In 1,4-dioxane; water; at 90℃; for 2h;Inert atmosphere; 6-bromoharmane (635 mg, 2.43 mmol) and 3-(N-Boc)-aminomethylphenyl boronic acid (732 mg, 2.92 mmol) were combined in deoxygenated dioxane (30 mL).A potassium phosphate solution (1.55 g, 7.29 mmol in 6 mL deoxygenated water) was added to the reaction mixture. The reaction mixture was stirred rapidly under argon. PdCl2dppf (177.8 mg, 0:243 mmol) was then added and the reaction mixture transferred to a pre-heated oil bath and stirred rapidly under argon at 90C. After 2 hours TLC, analysis indicated that all starting material had been consumed.The reaction was allowed to cool to room temperature and diluted with ethyl acetate (100 mL). This mixture was filtered through celite and washed with additional ethyl acetate. The organics were washed with water and twice with brine, dried over MgS04 and filtered and the solvent removed under reduced pressure. The residue was purified over silica (1 : 1 heptane/ethyl acetate to 10 % methanol / ethyl acetate) to give N-Boc-(3-(l -methyl-9H-pyrido[3,4-b]indol-6-yl)phenyl)methanamine (780 mg, 2.02 mmol), which was then dissolved in dioxane (10 mL). 4N HC1 in dioxane (50 mL) was added to this solution and the reaction mixture was stirred at room temperature. After 30 minutes, a thick yellow precipitate was formed and was then collected by suction filtration, washed with dioxane and dried in a vacuum oven to give (3-(l -methyl-9H-pyrido[3,4-b]indol-6-yl)phenyl)methanamine (710 mg).(3-(l -methyl-9H-pyrido[3,4-b]indol-6-yl)phenyl)methanamine (50 mg, 0.17 mmol) was suspended in dichloromethane (4 mL) and DIPEA (91 μ, 0.52 mmol) at room temperature. The respective isocyanate was added to this mixture and the reactions stirred at room temperature for 1 hour. A precipitate was formed and was collected by suction filtration to give the desired products.The following compounds were prepared using this procedure:l -ethyl-3-(3-(l-methyl-9H-pyrido[3,4-b]indol-6-yl)benzyl)urea (E41 ; 31 mg)
  • 29
  • [ 1429313-61-0 ]
  • [ 199609-62-6 ]
  • [ 1429313-71-2 ]
YieldReaction ConditionsOperation in experiment
71% With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); XPhos; In 1,4-dioxane; water; at 80℃; for 18h;Inert atmosphere; A mixture of 1 ,4-dioxane and water (3:1 , 9.36 ml) was degassed by bubbling nitrogen gas through the mixture. Intermediate 62 (2.00 g, 3.12 mmol), [3-[(tert- butoxycarbonylamino)methyl]phenyl]boronic acid (820 mg, 3.28 mmol), tetrakis(triphenylphosphine)palladium(0) (70 mg, 0.06 mmol), 2-dicyclohexylphosphino-2',4',6'- triisopropylbiphenyl (Xphos) (1 19 mg, 0.25 mmol) and potassium phosphate tribasic (3.307 g, 5 eq.) were added and the mixture was stirred under nitrogen gas at 80C for 18 hours. The reaction mixture was cooled and the solvent was removed under reduced pressure. Ethyl acetate was added and the organic layer was washed with water. The organic layer was dried, filtered and the solvent was removed under reduced pressure. The residue was purified by flash column chromatography over silica gel using heptane and ethyl acetate as eluents (gradient elution from 0% to 50% ethyl acetate). The product fractions were collected and the solvent was removed under reduced pressure.Yield: 1 .70 g of intermediate 72 (71 %)
71% With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); XPhos; In 1,4-dioxane; water; at 80℃; for 18h;Inert atmosphere; Preparation of Intermediate 72 A mixture of 1,4-dioxane and water (3:1, 9.36 ml) was degassed by bubbling nitrogen gas through the mixture. Intermediate 62 (2.00 g, 3.12 mmol), [3-[(tert-butoxycarbonylamino)methyl]phenyl]boronic acid (820 mg, 3.28 mmol), tetrakis(triphenylphosphine)palladium(0) (70 mg, 0.06 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) (119 mg, 0.25 mmol) and potassium phosphate tribasic (3.307 g, 5 eq.) were added and the mixture was stirred under nitrogen gas at 80 C. for 18 hours. The reaction mixture was cooled and the solvent was removed under reduced pressure. Ethyl acetate was added and the organic layer was washed with water. The organic layer was dried, filtered and the solvent was removed under reduced pressure. The residue was purified by flash column chromatography over silica gel using heptane and ethyl acetate as eluents (gradient elution from 0% to 50% ethyl acetate). The product fractions were collected and the solvent was removed under reduced pressure. [1066] Yield: 1.70 g of intermediate 72 (71%)
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Historical Records

Technical Information

• Acyl Group Substitution • Baeyer-Villiger Oxidation • Barbier Coupling Reaction • Baylis-Hillman Reaction • Bouveault-Blanc Reduction • Bucherer-Bergs Reaction • Buchwald-Hartwig C-N Bond and C-O Bond Formation Reactions • Catalytic Hydrogenation • Chan-Lam Coupling Reaction • Clemmensen Reduction • Complex Metal Hydride Reductions • Corey-Bakshi-Shibata (CBS) Reduction • Corey-Chaykovsky Reaction • Ester Cleavage • Fischer Indole Synthesis • Grignard Reaction • Henry Nitroaldol Reaction • Horner-Wadsworth-Emmons Reaction • Hydride Reductions • Lawesson's Reagent • Leuckart-Wallach Reaction • Mannich Reaction • McMurry Coupling • Meerwein-Ponndorf-Verley Reduction • Nomenclature of Ethers • Passerini Reaction • Paternò-Büchi Reaction • Petasis Reaction • Peterson Olefination • Pictet-Spengler Tetrahydroisoquinoline Synthesis • Preparation of Aldehydes and Ketones • Preparation of Amines • Preparation of Ethers • Prins Reaction • Reactions of Aldehydes and Ketones • Reactions of Amines • Reactions of Benzene and Substituted Benzenes • Reactions of Ethers • Reactions with Organometallic Reagents • Reformatsky Reaction • Robinson Annulation • Schlosser Modification of the Wittig Reaction • Schmidt Reaction • Specialized Acylation Reagents-Carbodiimides and Related Reagents • Specialized Acylation Reagents-Ketenes • Specialized Acylation Reagents-Vilsmeier Reagent • Stobbe Condensation • Tebbe Olefination • Ugi Reaction • Wittig Reaction • Wolff-Kishner Reduction

Categories

Related Functional Groups of
[ 199609-62-6 ]

Organoborons

Chemical Structure| 489446-42-6

A426540 [489446-42-6]

(4-(((tert-Butoxycarbonyl)amino)methyl)phenyl)boronic acid

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Chemical Structure| N/A

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(3-(((tert-Butoxycarbonyl)(methyl)amino)methyl)phenyl)boronic acid

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Aryls

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(4-(((tert-Butoxycarbonyl)amino)methyl)phenyl)boronic acid

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Amides

Chemical Structure| 489446-42-6

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(4-(((tert-Butoxycarbonyl)amino)methyl)phenyl)boronic acid

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Chemical Structure| N/A

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Amines

Chemical Structure| 489446-42-6

A426540 [489446-42-6]

(4-(((tert-Butoxycarbonyl)amino)methyl)phenyl)boronic acid

Similarity: 0.98

Chemical Structure| N/A

A253937 [N/A]

(3-(((tert-Butoxycarbonyl)(methyl)amino)methyl)phenyl)boronic acid

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