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[ CAS No. 1263291-41-3 ] {[proInfo.proName]}

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Chemical Structure| 1263291-41-3
Chemical Structure| 1263291-41-3
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Product Details of [ 1263291-41-3 ]

CAS No. :1263291-41-3 MDL No. :MFCD19705414
Formula : C10H14O Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 150.22 Pubchem ID :-
Synonyms :

Safety of [ 1263291-41-3 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P264-P280-P302+P352-P305+P351+P338-P332+P313-P337+P313-P362 UN#:N/A
Hazard Statements:H315-H319 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1263291-41-3 ]

* 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 [ 1263291-41-3 ]

[ 1263291-41-3 ] Synthesis Path-Downstream   1~84

  • 1
  • ((1R,8S,9r)-4,5-dibromobicyclo[6.1.0]nonan-9-yl)methanol [ No CAS ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
65% With potassium <i>tert</i>-butylate at 80℃; for 2h;
59% With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 75℃; for 2.16667h; Inert atmosphere;
53.7% With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 66℃; for 2.16667h;
128 mg With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; Inert atmosphere; Reflux;
With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 70℃; for 2h; Inert atmosphere;
With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 70℃; for 2h;
333 mg With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 85℃; for 16h;
With potassium <i>tert</i>-butylate In tetrahydrofuran

Reference: [1]Li, Xu; Liu, Zhengkun; Dong, Shouliang [RSC Advances, 2017, vol. 7, # 70, p. 44470 - 44473]
[2]Bultman, Max J.; Huang, Rui; Lewis, Jared C.; Li, Ying; Roux, Benoit; Upp, David M. [Angewandte Chemie - International Edition, 2021, vol. 60, # 44, p. 23672 - 23677][Angew. Chem., 2021, vol. 133, # 44, p. 23865 - 23870]
[3]Li, Fahui; Dong, Jianshu; Hu, Xiaosong; Gong, Weimin; Li, Jiasong; Shen, Jing; Tian, Huifang; Wang, Jiangyun [Angewandte Chemie - International Edition, 2015, vol. 54, # 15, p. 4597 - 4602][Angew. Chem., 2015, vol. 127, # 15, p. 4680 - 4685,6]
[4]Dommerholt, Jan; Schmidt, Samuel; Temming, Rinske; Hendriks, Linda J. A.; Rutjes, Floris P. J. T.; Van Hest, Jan C. M.; Lefeber, Dirk J.; Friedl, Peter; Van Delft, Floris L. [Angewandte Chemie - International Edition, 2010, vol. 49, # 49, p. 9422 - 9425]
[5]Gobbo, Pierangelo; Gunawardene, Praveen; Luo, Wilson; Workentin, Mark S. [Synlett, 2015, vol. 26, # 9, p. 1169 - 1174]
[6]Gobbo, Pierangelo; Romagnoli, Tommaso; Barbon, Stephanie M.; Price, Jacquelyn T.; Keir, Jennifer; Gilroy, Joe B.; Workentin, Mark S. [Chemical Communications, 2015, vol. 51, # 30, p. 6647 - 6650]
[7]Horner, Katherine A.; Valette, Nathalie M.; Webb, Michael E. [Chemistry - A European Journal, 2015, vol. 21, # 41, p. 14376 - 14381]
[8]Gential, Geoffroy P.P.; Ho, Nataschja I.; Chiodo, Fabrizio; Meeuwenoord, Nico; Ossendorp, Ferry; Overkleeft, Herman S.; van der Marel, Gijs A.; Filippov, Dmitri V. [Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 15, p. 3641 - 3645]
  • 2
  • [ 1263291-41-3 ]
  • [ 622-79-7 ]
  • rac-((5aR,6R,6aS)-1-benzyl-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
97% In chloroform-d1 at 20℃; for 25h; Inert atmosphere;
95% In water; acetonitrile at 20℃; for 16h;
  • 3
  • [ 1263291-41-3 ]
  • C32H36N2O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: triethylamine / acetonitrile / 3 h / 0 - 25 °C / Inert atmosphere 2: N-ethyl-N,N-diisopropylamine / N,N-dimethyl-formamide / 14 h / 25 °C / Inert atmosphere
  • 4
  • [ 1263291-41-3 ]
  • [ 1384100-45-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: triethylamine / acetonitrile / 3 h / 0 - 25 °C / Inert atmosphere 2: N-ethyl-N,N-diisopropylamine / N,N-dimethyl-formamide / 14 h / 25 °C / Inert atmosphere 3: polymer-bound piperazine / dichloromethane / 4 h / 25 °C / Inert atmosphere
  • 5
  • [ 1263291-41-3 ]
  • [ 1360467-31-7 ]
  • C29H34N6O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% In methanol at 25℃; for 0.05h; Inert atmosphere;
  • 6
  • [ 74124-79-1 ]
  • [ 1263291-41-3 ]
  • 1-([(1R,8S,9s)-bicyclo[6.1.0]non-4-yn-9-ylmethoxy]carbonyl}oxy)pyrrolidine-2,5-dione [ No CAS ]
YieldReaction ConditionsOperation in experiment
With triethylamine In acetonitrile at 0 - 25℃; for 3h; Inert atmosphere;
  • 7
  • [ 1263291-41-3 ]
  • [ 7693-46-1 ]
  • [ 1380006-72-3 ]
YieldReaction ConditionsOperation in experiment
89% With pyridine; In dichloromethane; at 20℃; for 0.5h; Example 1 : (1 ff,8S,9ff)-Bicyclo[6.1.0]non- - n-9-ylmethyl (4-nitrophenyl) carbonate (exo-13) To a solution of exo-12 (400 mg, 2.66 mmol) in CH2CI2 (20 mL) was added pyridine (540 μ, 6.70 mmol) and 4-nitrophenyl chloroformate (590 mg, 2.93 mmol). After stirring at rt for 30 min the reaction mixture was quenched with saturated NH4CI solution and extracted with CH2CI2 (3 x 20 mL). The combined organic layers were dried with MgS04 and concentrated in vacuo. The crude product was purified by column chromatography (hexanes: EtOAC, 4: 1 ) to afford exo-13 as a colourless oil, that solidified overnight (746 mg, 2.66 mmol, 89%). Rf 0.8 (hexanes: EtOAC, 2: 1 ); 1H NMR (500 MHz; CDCI3) δ 8.28 (2 H, d, J 9.2), 7.39 (2 H, d, J 9.2), 4.22 (2 H, d, J 6.9), 2.47-2.44 (2 H, m), 2.34-2.28 (2 H, m), 2.21 -2.17 (2 H, m), 1 .44-1 .40 (2 H, m), 0.88- 0.82 (3 H, m).
84% With pyridine; In dichloromethane; at 20℃; for 4h;Inert atmosphere; (lR,8S,9S)-Bicyclo[6.1.0]non-4-yn-9-yl methanol (800 mg, 5.3 mmol) was dissolved in DCM (125 mL) at room temperature under N2 atmosphere. Pyridine (1.22 mL, 15.9 mmol) and 4-nitrophenyl chloroformate (1.75 g, 8.74 mmol) were added thereto. After the mixture was stirred for 4 hours at the same temperature, the reaction was quenched by the addition of saturated NH4CI solution (100 mL) and extracted with EA (100 mL x 4). The organic layer was dried over Na2S04, filtered and concentrated in vacuo. The residue was purified by column chromatography (Hex: EA = 10: 1) to obtain compound BCN-PNP (1.34 g, 84 %) as white solid.1H NMR (600 MHz, CDCl3) δ 8.29 (d, J= 9 Hz, 2H), 7.39 (d, J= 9 Hz, 2H), 4.41 (d, J = 8.4 Hz, 2H), 2.36 - 2.24 (m, 6H), 1.62 - 1.55 (m, 2H), 1.53 - 1.49 (m, 1H), 1.07 (t, J= 10.2 Hz, 2H).
  • 8
  • [ 1263291-41-3 ]
  • [ 1419002-90-6 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: pyridine / dichloromethane / 0.5 h / 20 °C 2: triethylamine / N,N-dimethyl-formamide / 1 h / 20 °C
Multi-step reaction with 2 steps 1: pyridine / dichloromethane / 0.5 h / 20 °C 2: triethylamine / N,N-dimethyl-formamide / 1 h / 20 °C
  • 9
  • [ 1263291-41-3 ]
  • [ 1419002-92-8 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: pyridine / dichloromethane / 0.5 h / 20 °C 2: triethylamine / N,N-dimethyl-formamide / 1 h / 20 °C 3: N-ethyl-N,N-diisopropylamine / ethanol / 0.5 h / 20 °C
Multi-step reaction with 3 steps 1: pyridine / dichloromethane / 0.5 h / 20 °C 2: triethylamine / N,N-dimethyl-formamide / 1 h / 20 °C 3: N-ethyl-N,N-diisopropylamine / ethanol / 0.5 h / 20 °C
  • 10
  • [ 1263291-41-3 ]
  • [ 108-24-7 ]
  • [ 1539290-72-6 ]
YieldReaction ConditionsOperation in experiment
84% With dmap; triethylamine In dichloromethane at 0 - 20℃; for 3.5h;
  • 11
  • [ 1263291-41-3 ]
  • [ 98-88-4 ]
  • [ 1539290-73-7 ]
YieldReaction ConditionsOperation in experiment
82% With dmap; triethylamine In dichloromethane at 0 - 20℃; for 5.3h;
57% With dmap; triethylamine In dichloromethane at 0 - 20℃; for 4h; Inert atmosphere;
  • 12
  • [ 1263291-41-3 ]
  • [ 1616351-37-1 ]
  • [ 1616351-36-0 ]
YieldReaction ConditionsOperation in experiment
5% Stage #1: (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol; 5'-O-(2-cyanoethyl-N,N-diisopropylaminophosphino)-2',3'-O-(tertbutyldimethylsilyl)adenosine With benzyl tetrazol-5-yl sulphide In tetrahydrofuran at 20℃; for 1h; Stage #2: With tert.-butylhydroperoxide In tetrahydrofuran for 0.5h; Stage #3: With tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃;
  • 13
  • [ 860030-75-7 ]
  • [ 1263291-41-3 ]
  • [ 1616351-35-9 ]
YieldReaction ConditionsOperation in experiment
24% Stage #1: 2',3'-bis(tert-butyldimethylsilyl)guanosine-5'-O-(β-cyanoethyl-N,N-diisopropylphosphoramidite); (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol With benzyl tetrazol-5-yl sulphide In tetrahydrofuran at 20℃; for 1h; Stage #2: With tert.-butylhydroperoxide In tetrahydrofuran for 0.5h; Stage #3: With tetrabutyl ammonium fluoride In tetrahydrofuran at 20℃;
  • 15
  • [ 79549-89-6 ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: lithium aluminium tetrahydride / diethyl ether / 0.25 h / 0 - 20 °C / Inert atmosphere 2: bromine / dichloromethane / 0 °C 3: potassium <i>tert</i>-butylate / tetrahydrofuran / 2 h / 0 - 70 °C / Inert atmosphere
Multi-step reaction with 3 steps 1: lithium aluminium tetrahydride / tetrahydrofuran; diethyl ether 2: bromine / dichloromethane 3: potassium <i>tert</i>-butylate / tetrahydrofuran
Multi-step reaction with 3 steps 1: lithium aluminium tetrahydride / 0.5 h / 0 °C 2: bromine / 0.33 h / 0 °C 3: potassium <i>tert</i>-butylate / 2 h / 80 °C
With lithium aluminium tetrahydride; potassium <i>tert</i>-butylate; bromine

  • 17
  • [ 1263291-41-3 ]
  • C43H51N4O4(1+)*C2F3O2(1-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: pyridine / dichloromethane / 0.25 h / 20 °C / Inert atmosphere 2: N-ethyl-N,N-diisopropylamine / acetonitrile / 20 h / 20 °C / Inert atmosphere
  • 18
  • [ 111-78-4 ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: dirhodium tetraacetate / dichloromethane / 48 h / 0 - 20 °C / Inert atmosphere 2: lithium aluminium tetrahydride / diethyl ether / 0.25 h / 0 - 20 °C / Inert atmosphere 3: bromine / dichloromethane / 0 °C 4: potassium <i>tert</i>-butylate / tetrahydrofuran / 2 h / 0 - 70 °C / Inert atmosphere
Multi-step reaction with 4 steps 1: rhodium(II) acetate dimer / dichloromethane / 42 h / 0 - 20 °C 2: lithium aluminium tetrahydride / diethyl ether / 2 h / 0 - 20 °C 3: bromine / dichloromethane / Cooling with ice 4: potassium <i>tert</i>-butylate / tetrahydrofuran / 2.17 h / 0 - 66 °C
Multi-step reaction with 4 steps 1: copper acetylacetonate / ethyl acetate / Reflux 2: lithium aluminium tetrahydride / tetrahydrofuran; diethyl ether 3: bromine / dichloromethane 4: potassium <i>tert</i>-butylate / tetrahydrofuran
Multi-step reaction with 4 steps 1: dirhodium tetraacetate / 25 h / 20 °C 2: lithium aluminium tetrahydride / 0.5 h / 0 °C 3: bromine / 0.33 h / 0 °C 4: potassium <i>tert</i>-butylate / 2 h / 80 °C
Multi-step reaction with 2 steps 1: rhodium(II) acetate 2: lithium aluminium tetrahydride; bromine; potassium <i>tert</i>-butylate

  • 19
  • (1R,8S,9 ξ,Z)-ethylbicyclo[6.1.0]non-4-ene-9-carboxylate [ No CAS ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: lithium aluminium tetrahydride / diethyl ether / 2 h / 0 - 20 °C 2: bromine / dichloromethane / Cooling with ice 3: potassium <i>tert</i>-butylate / tetrahydrofuran / 2.17 h / 0 - 66 °C
Multi-step reaction with 3 steps 1: lithium aluminium tetrahydride / diethyl ether / 0 - 20 °C 2: bromine / dichloromethane / 0 °C 3: potassium <i>tert</i>-butylate / tetrahydrofuran / 2 h / 0 - 70 °C
Multi-step reaction with 3 steps 1: lithium aluminium tetrahydride / dichloromethane / 0 - 20 °C / Inert atmosphere 2: bromine / dichloromethane / 0 - 20 °C 3: potassium <i>tert</i>-butylate / tetrahydrofuran / 16 h / 0 - 85 °C
  • 20
  • (1RS,8SR,9RS,4Z)-bicyclo[6.1.0]non-4-ene-9-ylmethanol [ No CAS ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: bromine / dichloromethane / Cooling with ice 2: potassium <i>tert</i>-butylate / tetrahydrofuran / 2.17 h / 0 - 66 °C
Multi-step reaction with 2 steps 1: bromine / dichloromethane / 0 °C 2: potassium <i>tert</i>-butylate / tetrahydrofuran / 2 h / 0 - 70 °C
Multi-step reaction with 2 steps 1: bromine / dichloromethane / 0 - 20 °C 2: potassium <i>tert</i>-butylate / tetrahydrofuran / 16 h / 0 - 85 °C
  • 21
  • [ 1263291-41-3 ]
  • 5-(3-(4-((((1R,8S,9r)-bicyclo[6.1.0]non-4-yn-9-ylmethoxy)carbonyl)amino)butyl)thioureido)-2-(6-hydroxy-3-oxo-3H-xanthen-9-yl)benzoic acid [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: pyridine / dichloromethane / 0.67 h / 20 °C 2: triethylamine / N,N-dimethyl-formamide / 3 h / 20 °C
  • 22
  • [ 61117-58-6 ]
  • [ 1263291-41-3 ]
  • C16H14Co2O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% In dichloromethane at 20℃; for 1h; Glovebox; Inert atmosphere;
  • 23
  • C16H14Co2O7 [ No CAS ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
85% With trimethylamine-N-oxide In dichloromethane for 4h;
  • 24
  • [ 111-78-4 ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: dirhodium tetraacetate / dichloromethane / 48 h / Inert atmosphere 2: lithium aluminium tetrahydride / diethyl ether / 0 - 20 °C 3: bromine / dichloromethane / 0 °C 4: potassium <i>tert</i>-butylate / tetrahydrofuran / 2 h / 0 - 70 °C
Multi-step reaction with 4 steps 1: rhodium(II) acetate / dichloromethane / 12 h 2: lithium aluminium tetrahydride / dichloromethane / 0 - 20 °C / Inert atmosphere 3: bromine / dichloromethane / 0 - 20 °C 4: potassium <i>tert</i>-butylate / tetrahydrofuran / 16 h / 0 - 85 °C
  • 25
  • [ 1263291-41-3 ]
  • methyl (2S)-3-[2-(9-benzoyloxymethylbicyclo[6.1.0]nona[4,5-c]pyridyl)]-2-(N-(9-fluorenylmethoxycarbonyl)amino)propionate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: dmap; triethylamine / dichloromethane / 4 h / 0 - 20 °C / Inert atmosphere 2: dichloromethane / 16 h / 37 °C
  • 26
  • [ 1263291-41-3 ]
  • C35H57N3O6 [ No CAS ]
  • C45H71N3O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% In [D3]acetonitrile; water-d2 for 72h; Inert atmosphere;
  • 27
  • [ 641-57-6 ]
  • [ 1263291-41-3 ]
  • [ 201230-82-2 ]
  • C36H30O [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% In dichloromethane at 20℃; 1 Separate solutions of pure TPCPD (1) and pure exo-BCN (6a) (>95-98% by 1H- NMR) were prepared in HPLC-grade methanol (acetonitrile, 1 ,2-dichloroethane, dioxane) at room temperature. The stability of TPCPD in methanol (25 μΜ) was examined by monitoring its absorption maximum at 335 nm. The solutions containing TPCPD (1, 50 μΜ, 400 μ) and 18-fold excess of exo-BCN (6a, 900 μΜ, 400 μ) were added into quartz cuvettes, thoroughly mixed and sealed with a PTFE cap. All kinetic runs were triplicates. Curve fitting was operated in Prism5 software. [0265] The reaction between 1 and 6a (Scheme 8) leads to significant changes in the UV- Vis spectrum of TPCPD (30) due to its conversion to the cyclization product 31 (Figure la). Therefore, the reaction can be easily monitored. The reaction performed in dry methanol and the rate constant for the reaction between TPPD and BCN was found to be 0.50 M'V1 (Figure lb). Gas bubble formation was readily apparent, suggesting the release of CO as a byproduct. [0266] It was observed that the reaction rate between TPCPD and BCN was moderately sensitive to the reaction solvent. Methanol, acetonitrile, 1 ,2-dichloroethene (DCE), and dioxane were chosen for the kinetic studies. The reaction appears to be faster in polar solvents than in nonpolar solvents. For example, half-life (ti/2) of the reaction is 99 min in acetonitrile (Table 1), which is faster than in DCE (130 min), and in dioxane (282 min). The reaction in methanol was observed to be faster than in acetonitrile, which clearly indicates that the protic solvent has an enhancing effect on the reaction rate. In order to utilize the reaction under physiological conditions, the reaction rate was measured at physiological temperature, 37°C. The results are shown in Table 1. Table 1. Second order rate constants of TPCPD with BCN in different solvents. * All half-life va ues were determined for exo-BCN at 450 μΜ (6a). [0267] From Table 1 , it is observed that the second order rate constant at 37°C increased about 2 fold compared to the rate at room temperature, 23°C.
  • 28
  • [ 1263291-41-3 ]
  • [ 479-33-4 ]
  • C39H34O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% In dichloromethane at 20℃; for 0.0833333h; 1 To a solution of TPCPD (1) in CH2C12 (0.5 mL), exo-BCN (6a) in CH2C12 (0.5 mL) was added. The reaction was stirred at room temperature for 5 min. The progress of the reaction was monitored by TLC (hexane / ethyl Acetate 1 : 1, R product = 0.4). Upon completion, the reaction mixture was directly loaded on the flash column chromatography and purified using hexane:ethyl Acetate 10: 1 , to give a white solid product. (Yield: 94%). JH NMR (CDC13): δ 7.17-7.03 (m, 10H, Ph-H), 6.82- 6.70 (m, 10, Ph-H) 3.45 (d, J = 4.0 Hz, 2H, -CH2-OH), 2.84-2.77 (m, 2H, -CH2-C=C-), 2.71-2.65 (br, 2H, -CH2-C=C-), 2.25-2.22 (br, 1H, -CH-CH2OH), 1.53 (br, 2H, -C-CH-C-), 0.89-0.87 (br, 2H, -CH2-), 0.79-0.77 (br, 2H, - CH2-) 13C NMR (CDCI3) δ 195.9, 141.7, 140.9, 140.7, 140.3, 138.6, 131.4, 131.0, 130.5, 130.4, 127.2, 127.1,126.4, 126.2, 125.8, 124.9, 66.6, 30.7, 29.9, 22.6, 21.5. MS calcd. for C38H340 [M+Na]+ 529.2507, found 529.2491.
  • 29
  • [ 1263291-41-3 ]
  • [ 479-33-4 ]
  • [ 201230-82-2 ]
  • C38H34O [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 37℃; 1 Separate solutions of pure TPCPD (1) and pure exo-BCN (6a) (>95-98% by 1H- NMR) were prepared in HPLC-grade methanol (acetonitrile, 1 ,2-dichloroethane, dioxane) at room temperature. The stability of TPCPD in methanol (25 μΜ) was examined by monitoring its absorption maximum at 335 nm. The solutions containing TPCPD (1, 50 μΜ, 400 μ) and 18-fold excess of exo-BCN (6a, 900 μΜ, 400 μ) were added into quartz cuvettes, thoroughly mixed and sealed with a PTFE cap. All kinetic runs were triplicates. Curve fitting was operated in Prism5 software. [0265] The reaction between 1 and 6a (Scheme 8) leads to significant changes in the UV- Vis spectrum of TPCPD (30) due to its conversion to the cyclization product 31 (Figure la). Therefore, the reaction can be easily monitored. The reaction performed in dry methanol and the rate constant for the reaction between TPPD and BCN was found to be 0.50 M'V1 (Figure lb). Gas bubble formation was readily apparent, suggesting the release of CO as a byproduct. [0266] It was observed that the reaction rate between TPCPD and BCN was moderately sensitive to the reaction solvent. Methanol, acetonitrile, 1 ,2-dichloroethene (DCE), and dioxane were chosen for the kinetic studies. The reaction appears to be faster in polar solvents than in nonpolar solvents. For example, half-life (ti/2) of the reaction is 99 min in acetonitrile (Table 1), which is faster than in DCE (130 min), and in dioxane (282 min). The reaction in methanol was observed to be faster than in acetonitrile, which clearly indicates that the protic solvent has an enhancing effect on the reaction rate. In order to utilize the reaction under physiological conditions, the reaction rate was measured at physiological temperature, 37°C. The results are shown in Table 1. Table 1. Second order rate constants of TPCPD with BCN in different solvents. * All half-life va ues were determined for exo-BCN at 450 μΜ (6a). [0267] From Table 1 , it is observed that the second order rate constant at 37°C increased about 2 fold compared to the rate at room temperature, 23°C.
  • 30
  • C10H16O [ No CAS ]
  • [ 1263166-90-0 ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
Stage #1: C10H16O With bromine In dichloromethane at 20℃; for 0.5h; Stage #2: With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 21h; Reflux; Overall yield = 1.11 g;
  • 31
  • [ 1263291-41-3 ]
  • C20H28O2S2 [ No CAS ]
  • C22H32O2S [ No CAS ]
  • C20H28O2S2 [ No CAS ]
  • C22H32O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sulfur; hydridotetakis(triphenylphosphine)rhodium(I); 1,2-bis-(diphenylphosphino)ethane In butanone for 3h; Inert atmosphere; Reflux; 1,2,3,4,5,6,8,9,10,11,12,13-Dodecahydrodicycloocta[1,4]dithiin(3a)15 and 1,2,3,4,5,6,8,9,10,11,12,13-Dodecahydrodicycloocta[b,d]thiophene (4a);15 Typical Procedure General procedure: In a two-necked flask equipped with a reflux condenser were placed RhH(PPh3)4(14.4 mg, 5 mol%), 1,2-bis(diphenylphosphino)ethane (dppe, 10.0 mg, 10 mol%), sulfur (2; 9.6 mg, 0.3 mmol), and cyclooctyne (1a; 92.0 μL, 0.75 mmol) in 2-butanone (1.0 mL) under an argon atmosphere, and the solution was heated at reflux for 3 h. The solvent was removed under reduced pressure, and the residue was purified by flash column chromatography on silica gel to give 3a and 4a.
  • 32
  • [ 1263291-41-3 ]
  • N-[(1R,8S,9S)-bicyclo[6.1.0]non-4-yn-9-ylmethyloxycarbonyl]-1,8-diamino-3,6-dioxaoctane [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: dichloromethane 2: triethylamine / N,N-dimethyl-formamide
  • 33
  • [ 1263291-41-3 ]
  • C49H65N4O5(1+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: dichloromethane 2: triethylamine / N,N-dimethyl-formamide 3: N-ethyl-N,N-diisopropylamine / N,N-dimethyl-formamide
  • 34
  • [ 1263291-41-3 ]
  • C42H48N4O8 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1.1: dichloromethane 2.1: triethylamine / N,N-dimethyl-formamide 3.1: acetic acid; sulfuric acid / Reflux 3.2: 20 °C 3.3: 20 °C
  • 35
  • [ 1263291-41-3 ]
  • C35H57N3O6 [ No CAS ]
  • C45H71N3O7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% In [D3]acetonitrile; water-d2 for 72h; To a solution of 1 (1.0 mg, 1.6 .imol, 1 equiv) in 1:2 CD3CN/D20 (0.5 mL) was added cyclooctyne (2.0 mg, 13 pmol, 8 equiv) . After 72h, the reaction was directly purified by silica gel flash column chromatography (100% EtOAc to elute cyclooctyne, then 10-15%MeOH/CH,C12 to elute product) affording triazole 26 (1.0 tug, 83% yield) . TLC Rf 0.42 (10% MeOH/CH2C12); XR (thin film) 3385 (bs), 2925, 1699, 1638, 1458, 1383, 1066, 732 crw’; ‘H N ‘H NMR (500 MHz,CDC13) ö 7.31 (dd, J = 16.0, 11.4 Hz, 1H, C4H), 6.59 Cdt, J = 16.9,10.7 Hz, 1H, C25H), 6.50 - 6.44 (in, 1H, C3H), 6.02 - 5.94 (m, 21-, C5H,C,4H), 5.56 (t, J = 10.3 Hz, 1H, CioH), 5.49 (d, J = 11.3 Hz, 1H, C,H),5.32 (t, J - 10.5 Hz, U-I, Ci,H), 5.26 (t, J 10.5 Hz, 1H, C23H), 5.17(dd, J = 16.8, 2.0 Hz, 1H, C26Ha), 5.09 (d, J = 10.2 Hz, 1H, C2GHb),4.93 (dd, J = 8.4, 2.5 Hz, 11-I, C21H), 4.79 (dt, J = 10.0, 5.4 Hz, 1H,C9H), 4.26 - 4.17 (m, 21-I, a-triazole), 3.99 - 3.90 (in, 1H, C7H), 3.60- 3.53 (m, 1H), 3.51 - 3.42 Cm, 2H, C19H), 3.27 (d, J = 7.9 Hz, 1H,C,,H), 3.09 (m, 1H), 3.04 - 2.94 (in, 1H, C22H), 2.90 - 2.80 (m, 2H),2.79 - 2.71 (in, 1H, C,,F{), 2.69 - 2.61 (in, 1H), 2.48 - 2.36 (in, 2H),2.25 - 2.18 (in, 1H, C6H), 1.90 - 1.85 (in, 1H, C20H); HRMS: Exact mass calcd for C45H72N307 [M+H1: 766.5370; found 766.5392 (FAB+)
  • 36
  • [ 1263291-41-3 ]
  • C10H12O [ No CAS ]
YieldReaction ConditionsOperation in experiment
95% With oxalyl dichloride; dimethyl sulfoxide; triethylamine at -78℃; for 5h;
  • 37
  • [ 1263291-41-3 ]
  • C11H14N2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: oxalyl dichloride; triethylamine; dimethyl sulfoxide / 5 h / -78 °C 2: lithium hexamethyldisilazane / tetrahydrofuran / 12 h / -40 - 20 °C
  • 38
  • [ 1263291-41-3 ]
  • C11H15NO2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: oxalyl dichloride; triethylamine; dimethyl sulfoxide / 5 h / -78 °C 2: lithium hexamethyldisilazane / tetrahydrofuran / 12 h / -40 - 20 °C 3: sodium hydroxide / 2 h / 80 °C
  • 39
  • [ 1263291-41-3 ]
  • C13H17NO3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: oxalyl dichloride; triethylamine; dimethyl sulfoxide / 5 h / -78 °C 2: lithium hexamethyldisilazane / tetrahydrofuran / 12 h / -40 - 20 °C 3: sodium hydroxide / 2 h / 80 °C 4: sodium hydroxide / 2 h / 20 °C
  • 40
  • [ 1263291-41-3 ]
  • C11H15NO2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: oxalyl dichloride; triethylamine; dimethyl sulfoxide / 5 h / -78 °C 2: lithium hexamethyldisilazane / tetrahydrofuran / 12 h / -40 - 20 °C 3: sodium hydroxide / 2 h / 80 °C 4: sodium hydroxide / 2 h / 20 °C 5: kidney acylase I / 48 h / 37 °C
  • 41
  • [ 1263291-41-3 ]
  • C23H30N4O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: oxalyl dichloride; triethylamine; dimethyl sulfoxide / 5 h / -78 °C 2: lithium hexamethyldisilazane / tetrahydrofuran / 12 h / -40 - 20 °C 3: sodium hydroxide / 2 h / 80 °C 4: sodium hydroxide / 2 h / 20 °C 5: kidney acylase I / 48 h / 37 °C 6: aq. phosphate buffer / 0.5 h / 20 °C
  • 42
  • [ 1263291-41-3 ]
  • C22H28N4O4 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: oxalyl dichloride; triethylamine; dimethyl sulfoxide / 5 h / -78 °C 2: lithium hexamethyldisilazane / tetrahydrofuran / 12 h / -40 - 20 °C 3: sodium hydroxide / 2 h / 80 °C 4: sodium hydroxide / 2 h / 20 °C 5: kidney acylase I / 48 h / 37 °C 6: aq. phosphate buffer / 0.5 h / 20 °C
  • 43
  • [ 1263291-41-3 ]
  • N-(3-(3-(((5-(azidomethyl)pyrimidin-2-yl)thio)methyl)-1,1,3,3-tetramethyldisiloxanyl)propyl)acetamide [ No CAS ]
  • C25H42N6O3SSi2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
63% at 20℃; 74 Example 74 A solution of (15.93 mg, 0.039 mmol) in 0.766 mL of a 3:1 mixture of acetonitrile/water was charged with (1R,8S,9 s)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (5.8 mg, 0.039 mmol) and stirred overnight at rt. The crude reaction mixture was concentrated in vacuo then purified by chromatography on silica gel, ISCO, 4 g gold cartridge [eluting wN-(3-(3-(((5-(azidomethyl)pyrimidin-2-yl)thio)methyl)-1,1,3,3-tetra methyl disiloxanyl)propyl)acetamideith 100% DCM to 5% (10% 7N NH3 in MeOH) in DCM] resulting in 13.7 mg, 63% yield of the title compound as a thick clear colorless oil. 1H NMR (CHLOROFORM-d, 400 MHz): δ (ppm) 8.38 (s, 2H), 5.60 (br s, 1H), 5.41 (s, 2H), 3.61-3.82 (m, 2H), 3.18-3.24 (m, 2H), 3.09-3.17 (m, 1H), 2.80-2.97 (m, 2H), 2.63 (ddd, J=16.1, 10.5, 3.4 Hz, 1H), 2.39 (s, 2H), 2.11-2.30 (m, 2H), 1.97 (s, 3H), 1.46-1.60 (m, 4H), 1.41 (br s, 1H), 1.26 (s, 1H), 1.20 (dt, J=16.5, 8.4 Hz, 1H), 1.04 (dtd, J=10.8, 8.9, 5.1 Hz, 1H), 0.76-0.97 (m, 2H), 0.49-0.58 (m, 2H), 0.20 (s, 6H), 0.08 (s, 6H), MS (ES+): m/z=563.45 [M+H]+; LCMS: tR=1.93 min [polar 3 min_1500].
  • 44
  • [ 1263291-41-3 ]
  • 3-(4-(((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)oxycarbonyl)piperazin-1-yl)-2,4,5-trichlorothiophene S,S-dioxide [ No CAS ]
  • ((1α,1aα,9aα)-6-(4-(((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)oxycarbonyl)piperazin-1-yl)-4,5,7-trichloro-1a,2,3,8,9,9a-hexahydrobenzo[a]cyclopropa[e]cycloocten-1-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% In methanol at 20℃; for 17h; Inert atmosphere; Conjugation of thiophene dioxide 7m with BCN derivative 2 To a solution of 3-(4-(((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)oxycarbonyl)piperazin-1-yl)-2,4,5-trichlorothiophene S,S-dioxide (7m) (53.2 mg, 92% purity, 94 μmol) dissolved in MeOH (2.0 mL) wasadded (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (2) (15.3 mg, 0.102 mmol) at room temperature.After stirring for 17 h at the same temperature, the mixture was concentrated under reduced pressure. Theresidue was purified by preparative TLC (EtOAc only) to give benzocyclooctene 19 (56.6 mg, 93% purity,87 μmol, 92%) as a colorless solid containing 2.7 wt% of CH2Cl2 and 4.7 wt% of n-hexane.
  • 45
  • [ 1263291-41-3 ]
  • 3-(4-(tert-butoxycarbonyl)piperazin-1-yl)-2,4,5-trichlorothiophene S,S-dioxide [ No CAS ]
  • C23H31Cl3N2O3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% In methanol at 20℃; for 24h; Inert atmosphere;
  • 46
  • [ 1263291-41-3 ]
  • [ 72448-17-0 ]
  • ((1α,1aα,9aα)-4,5,6,7-tetrachloro-1a,2,3,8,9,9a-hexahydrobenzo[a]cyclopropa[e]cycloocten-1-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% In methanol at 25℃; for 2h; Inert atmosphere; typical procedure for the Diels-Alder reaction between thiophene dioxide 7 and BCN derivative 2 To a solution of 2,3,4,5-tetrachlorothiophene S,S-dioxide (7e) (12.7 mg, 50.0 μmol) dissolved in MeOH(1.0 mL) was added (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (2) (11.2 mg, 74.6 μmol) at roomtemperature. After stirring for 2 h at the same temperature, the mixture was concentrated under reducedpressure. The residue was purified by preparative TLC (toluene/EtOAc = 4/1) to give benzocyclooctene 8e(15.8 mg, 46.5 μmol, 93.0%) as a colorless solid.
  • 47
  • [ 1263291-41-3 ]
  • 2,5-dibromothiophene S,S-dioxide [ No CAS ]
  • ((1α,1aα,9aα)-4,7-dibromo-1a,2,3,8,9,9a-hexahydrobenzo[a]cyclopropa[e]cycloocten-1-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% In methanol at 25℃; for 2h; Inert atmosphere; typical procedure for the Diels-Alder reaction between thiophene dioxide 7 and BCN derivative 2 General procedure: To a solution of 2,3,4,5-tetrachlorothiophene S,S-dioxide (7e) (12.7 mg, 50.0 μmol) dissolved in MeOH(1.0 mL) was added (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (2) (11.2 mg, 74.6 μmol) at roomtemperature. After stirring for 2 h at the same temperature, the mixture was concentrated under reducedpressure. The residue was purified by preparative TLC (toluene/EtOAc = 4/1) to give benzocyclooctene 8e(15.8 mg, 46.5 μmol, 93.0%) as a colorless solid.
  • 48
  • [ 1263291-41-3 ]
  • 2,5-bis(4-(trifluoromethyl)phenyl)thiophene 1,1-dioxide [ No CAS ]
  • ((1α,1aα,9aα)-4,7-bis(4-(trifluoromethyl)phenyl)-1a,2,3,8,9,9a-hexahydrobenzo[a]cyclopropa[e]cycloocten-1-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
53% In methanol at 20℃; for 2h; Inert atmosphere; typical procedure for the Diels-Alder reaction between thiophene dioxide 7 and BCN derivative 2 General procedure: To a solution of 2,3,4,5-tetrachlorothiophene S,S-dioxide (7e) (12.7 mg, 50.0 μmol) dissolved in MeOH(1.0 mL) was added (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (2) (11.2 mg, 74.6 μmol) at roomtemperature. After stirring for 2 h at the same temperature, the mixture was concentrated under reducedpressure. The residue was purified by preparative TLC (toluene/EtOAc = 4/1) to give benzocyclooctene 8e(15.8 mg, 46.5 μmol, 93.0%) as a colorless solid.
  • 49
  • [ 52819-14-4 ]
  • [ 1263291-41-3 ]
  • ((1α,1aα,9aα)-5,6-dichloro-1a,2,3,8,9,9a-hexahydrobenzo[a]cyclopropa[e]cycloocten-1-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
96% In methanol at 25℃; for 2h; Inert atmosphere; typical procedure for the Diels-Alder reaction between thiophene dioxide 7 and BCN derivative 2 General procedure: To a solution of 2,3,4,5-tetrachlorothiophene S,S-dioxide (7e) (12.7 mg, 50.0 μmol) dissolved in MeOH(1.0 mL) was added (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (2) (11.2 mg, 74.6 μmol) at roomtemperature. After stirring for 2 h at the same temperature, the mixture was concentrated under reducedpressure. The residue was purified by preparative TLC (toluene/EtOAc = 4/1) to give benzocyclooctene 8e(15.8 mg, 46.5 μmol, 93.0%) as a colorless solid.
  • 50
  • [ 1263291-41-3 ]
  • [ 89088-96-0 ]
  • ((1α,1aα,9aα)-5,6-dibromo-1a,2,3,8,9,9a-hexahydrobenzo[a]cyclopropa[e]cycloocten-1-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% In methanol at 25℃; for 2h; Inert atmosphere; typical procedure for the Diels-Alder reaction between thiophene dioxide 7 and BCN derivative 2 General procedure: To a solution of 2,3,4,5-tetrachlorothiophene S,S-dioxide (7e) (12.7 mg, 50.0 μmol) dissolved in MeOH(1.0 mL) was added (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (2) (11.2 mg, 74.6 μmol) at roomtemperature. After stirring for 2 h at the same temperature, the mixture was concentrated under reducedpressure. The residue was purified by preparative TLC (toluene/EtOAc = 4/1) to give benzocyclooctene 8e(15.8 mg, 46.5 μmol, 93.0%) as a colorless solid.
  • 51
  • [ 1263291-41-3 ]
  • [ 143810-43-9 ]
  • ((1α,1aα,9aα)-4,7-diiodo-1a,2,3,8,9,9a-hexahydrobenzo[a]cyclopropa[e]cycloocten-1-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% In methanol at 25℃; for 2h; Inert atmosphere; typical procedure for the Diels-Alder reaction between thiophene dioxide 7 and BCN derivative 2 General procedure: To a solution of 2,3,4,5-tetrachlorothiophene S,S-dioxide (7e) (12.7 mg, 50.0 μmol) dissolved in MeOH(1.0 mL) was added (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (2) (11.2 mg, 74.6 μmol) at roomtemperature. After stirring for 2 h at the same temperature, the mixture was concentrated under reducedpressure. The residue was purified by preparative TLC (toluene/EtOAc = 4/1) to give benzocyclooctene 8e(15.8 mg, 46.5 μmol, 93.0%) as a colorless solid.
  • 52
  • [ 1263291-41-3 ]
  • [ 72524-90-4 ]
  • ((1α,1aα,9aα)-4,5,6,7-tetrabromo-1a,2,3,8,9,9a-hexahydrobenzo[a]cyclopropa[e]cycloocten-1-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
100% In methanol at 25℃; for 2h; Inert atmosphere; typical procedure for the Diels-Alder reaction between thiophene dioxide 7 and BCN derivative 2 General procedure: To a solution of 2,3,4,5-tetrachlorothiophene S,S-dioxide (7e) (12.7 mg, 50.0 μmol) dissolved in MeOH(1.0 mL) was added (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (2) (11.2 mg, 74.6 μmol) at roomtemperature. After stirring for 2 h at the same temperature, the mixture was concentrated under reducedpressure. The residue was purified by preparative TLC (toluene/EtOAc = 4/1) to give benzocyclooctene 8e(15.8 mg, 46.5 μmol, 93.0%) as a colorless solid.
  • 53
  • [ 1263291-41-3 ]
  • C35H29Cl3N3O5PS [ No CAS ]
  • ((1α,1aα,9aα)-4,5,7-trichloro-6-(4-(4-((2-(diphenylphosphoryl)benzoyl)aminomethyl)benzoyl)piperazin-1-yl)-1a,2,3,8,9,9ahexahydrobenzo[a]cyclopropa[e]cycloocten-1-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
37.2 mg In tetrahydrofuran; water at 20℃; for 24h; Inert atmosphere; Sequential conjugation using bisreactive platform 7l via the Staudinger-Bertozzi ligation withphosphine 20 followed by the Diels-Alder reaction with BCN derivative 2 To a solution of 3-(4-(4-(azidomethyl)benzoyl)piperazin-1-yl)-2,4,5-trichlorothiophene S,S-dioxide (7l)(23.2 mg, 50.1 μmol) dissolved in THF (1.0 mL) and H2O (0.10 mL) was added 2-(diphenylphosphanyl)benzoic acid methyl ester (20) (23.8 mg, 74.3 μmol). After stirring for 24 h, to themixture was added (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol (2) (11.2 mg, 74.6 μmol). After stirringfor 24 h at the same temperature, the mixture was concentrated under reduced pressure. The residue waspurified by preparative TLC (CH2Cl2/MeOH = 14/1) to give benzocyclooctene 21 (37.2 mg, 45.0 μmol,89.8% in 2 steps) as a colorless solid.
  • 54
  • [ 1263291-41-3 ]
  • 5'-O-(triisopropylsilyl)-3'-O-azidomethyl-5-(perylen-3-ylethynyl)-2'-deoxyuridine [ No CAS ]
  • C42H37N5O6 [ No CAS ]
  • C42H37N5O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol; 5'-O-(triisopropylsilyl)-3'-O-azidomethyl-5-(perylen-3-ylethynyl)-2'-deoxyuridine In dimethyl sulfoxide for 0.0833333h; Stage #2: With tetrabutyl ammonium fluoride; water In dimethyl sulfoxide at 20℃; Overall yield = 70 %; Overall yield = 50 mg; 4.2.7 General procedure for the copper-free cycloaddition reaction of 5 with the corresponding bicyclononyne derivative General procedure: To a solution of 5 (70mg, 0.10mmol) in DMSO (2mL) bicyclononyne derivative (16mg, 0.11mmol) was added and the resulting mixture was stirred for 5min. The solution was poured in the mixture of EtOAc (50mL) and water (20mL), the organic layer was washed with water (2×20mL), dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by column chromatography (0→30% EtOAc in CH2Cl2). The intermediate product obtained was dissolved in DMSO (2mL) and TBAF·3H2O was added (34mg, 0.11mmol). After stirring overnight the mixture was diluted with H2O (10mL) and placed into the refrigerator (+4°C) for several hours. The solid precipitated was filtered, washed with water (2×5mL), diethyl ether (2×5mL) and hexane (2×5mL), and then dried in vacuum affording the corresponding product 8 as a mixture of inseparable diastereomers. 4.2.7.1 8a was prepared from (1R,8S,9s)-bicyclo[6.1.0]non-4-yn-9-ylmethanol; yield 50mg (70%); amorphous orange solid. 1H NMR (600MHz, DMSO-d6): δ ppm 11.79 (s, 1H), 8.46 (d, J=4.0Hz, 1H), 8.43 (d, J=7.6Hz, 1H), 8.40-8.32 (m, 3H), 8.28 (d, J=8.3Hz, 1H), 7.84-7.79 (m, 2H), 7.71-7.65 (m, 2H), 7.55 (t, J=7.8Hz, 2H), 6.11-6.09 (m, 1H), 5.76 (s, 2H), 5.31 (br s, 1H), 4.39 (br s, 1H), 4.29-4.23 (m, 1H), 3.95-3.90 (m, 1H), 3.65 (m, J=11.2Hz, 1H), 3.56 (d, J=11.2Hz, 1H), 3.29-3.23 (m, 2H), 3.02-2.93 (m, 2H), 2.77-2.68 (m, 2H), 2.35-2.28 (m, 1H), 2.27-2.21 (m, 1H), 2.19-2.03 (m, 2H), 1.39-1.29 (m, 2H), 0.75-0.64 (m, 2H), 0.60-0.53 (m, 1H). 13C NMR (151MHz, DMSO-d6): δ ppm 161.37, 149.32, 144.86 & 144.75 (diastereomers), 143.36 & 143.32 (diastereomers), 134.10, 134.04 & 133.98 (diastereomers), 133.68, 131.09, 130.88, 130.37, 130.01, 129.72, 128.54, 128.23, 127.79, 127.68, 127.51, 126.91, 126.86, 125.69, 121.49, 121.30, 121.17, 120.17, 119.33, 98.55, 90.68, 88.61, 85.05 & 84.92 (diastereomers), 84.95 & 84.87 (diastereomers), 77.96 & 77.58 (diastereomers), 75.24 & 75.07 (diastereomers), 63.93, 60.93 & 60.87 (diastereomers), 37.20 & 37.13 (diastereomers), 27.16 & 27.12 (diastereomers), 26.68 & 26.63 (diastereomers), 25.90, 25.29 & 25.23 (diastereomers), 21.81 & 21.79 (diastereomers), 21.38 & 21.31(diastereomers), 21.22 & 21.20 (diastereomers). HRMS (ESI) m/z: calcd for C42H38N5O6+ [M+H]+: 708.2817; found 708.2807; calcd for C42H37N5NaO6+ [M+Na]+: 730.2636; found 730.2629; calcd for C42H37KN5O6+ [M+K]+: 746.2375; found 746.2379.
  • 55
  • [ 38556-93-3 ]
  • [ 1263291-41-3 ]
  • ((5aα,6α,6aα)-1-(4-(ethoxycarbonyl)phenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
97.5% In methanol at 20℃; for 4h; Inert atmosphere;
  • 56
  • [ 1263291-41-3 ]
  • [ 1310822-76-4 ]
  • ((5aα,6α,6aα)-1-(3-azido-5-(methoxycarbonyl)benzyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
  • ((5aα,6α,6aα)-1-(3-(azidomethyl)-5-(methoxycarbonyl)phenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
  • methyl 3-((5aα,6α,6aα)-6-(hydroxymethyl)-5,5a,6,6a,7,8-hexahydrocyclopropa[5,6]cyclo- octa[1,2-d][1,2,3]triazol-1(4H)-yl)-5-(((5aβ,6β,6aβ)-6-(hydroxymethyl)-5,5a,6,6a,7,8-hexahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-1(4H)-yl)methyl)benzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 52.6% 2: 20% 3: 7.4% In methanol at 20℃; for 24h; Inert atmosphere;
  • 57
  • [ 1263291-41-3 ]
  • [ 2101-87-3 ]
  • ((5aα,6α,6aα)-1-(4-methoxyphenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 20℃; for 4h; Inert atmosphere;
  • 58
  • [ 85862-68-6 ]
  • [ 1263291-41-3 ]
  • ((5aα,6α,6aα)-1-(3,5-dimethoxyphenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 20℃; for 4h; Inert atmosphere;
  • 59
  • [ 53694-87-4 ]
  • [ 1263291-41-3 ]
  • ((5aα,6α,6aα)-1-(4-iodophenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 20℃; for 4h; Inert atmosphere;
  • 60
  • [ 1263291-41-3 ]
  • C25H36N7O2P [ No CAS ]
  • ((5aα,6α,6aα)-1-(3-azido-5-(methoxycarbonyl)benzyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
32.8 mg Stage #1: (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol; C25H36N7O2P In methanol at 20℃; for 24h; Inert atmosphere; Stage #2: With sulfur In methanol at 20℃; for 24h; Inert atmosphere;
  • 61
  • [ 3296-07-9 ]
  • [ 1263291-41-3 ]
  • ((5aα,6α,6aα)-1-(2-chlorophenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 20℃; for 4h; Inert atmosphere;
  • 62
  • [ 1263291-41-3 ]
  • [ 94341-53-4 ]
  • ((5aα,6α,6aα)-1-(4-(methoxycarbonyl)benzyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 20℃; for 4h; Inert atmosphere;
  • 63
  • [ 53053-08-0 ]
  • [ 1263291-41-3 ]
  • ((5aα,6α,6aα)-1-(4-(succinimidyloxycarbonyl)phenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 20℃; for 4h; Inert atmosphere;
  • 64
  • [ 1263291-41-3 ]
  • 4-(propargylaminocarbonyl)phenyl azide [ No CAS ]
  • ((5aα,6α,6aα)-1-(4-(propargylaminocarbonyl)phenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 20℃; for 4h; Inert atmosphere;
  • 65
  • [ 1516-60-5 ]
  • [ 1263291-41-3 ]
  • ((5aα,6α,6aα)-1-(4-nitrophenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
In methanol at 20℃; for 4h; Inert atmosphere;
  • 66
  • [ 1263291-41-3 ]
  • [ 479-33-4 ]
  • C39H36O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
94% In dichloromethane at 20℃; for 0.0833333h; 1 To a solution of TPCPD (1) in CH2C12 (0.5 mL), exo-BCN (6a) in CH2C12 (0.5 mL) was added. The reaction was stirred at room temperature for 5 mm. The progress of the reaction was monitored by TLC (hexane / ethyl Acetate 1:1, R1 product = 0.4). Upon completion, the reaction mixture was directly loaded on the flash column chromatography and purified using hexane:ethyl acetate 10:1, to give a white solid product. (Yield: 94%). ‘HNIVIR (CDC13): 7.17-7.03 (m, 1OH, Ph-H), 6.82- 6.70 (m, 10, Ph-H) 3.45 (d, J = 4.0 Hz, 2H,-CH2-OH), 2.84-2.77 (m, 2H, -CH2-C=C-), 2.71-2.65 (br, 2H, -CH2-C=C-), 2.25-2.22 (br, 1H, -CH-CH2OH), 1.53 (br, 2H, -C-CH-C-), 0.89-0.87 (br, 2H, -CH2-), 0.79-0.77 (br, 2H, - CH2-) ‘3CNIVIR(CDC13) 195.9, 141.7, 140.9, 140.7, 140.3, 138.6, 131.4, 131.0, 130.5, 130.4, 127.2, 127.1,126.4, 126.2, 125.8, 124.9, 66.6, 30.7, 29.9, 22.6, 21.5. MS calcd. forC38H340 [M+Na] 529.2507, found 529.2491.
  • 67
  • [ 1263291-41-3 ]
  • [(1,3-bis(2,6-di-iso-propylphenyl)imidazol-2-ylidene)Au-(1-SCH2-2,5-Me2-4-N3CH2C6H2)] [ No CAS ]
  • C47H62AuN5OS [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% In dichloromethane at 20℃; for 12h; Inert atmosphere; Schlenk technique;
  • 68
  • [ 1263291-41-3 ]
  • 2,6-diisopropyl-4-pyrrolidinophenyl azide [ No CAS ]
  • (5aS,6S,6aR)-1-(2,6-diisopropyl-4-pyrrolidinophenyl)-6-(hydroxymethyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% In methanol at 20℃; for 2h;
  • 69
  • [ 1263291-41-3 ]
  • [ 136551-45-6 ]
  • C22H31N3O [ No CAS ]
YieldReaction ConditionsOperation in experiment
91.4% In methanol at 20℃; for 2h;
  • 70
  • [ 1263291-41-3 ]
  • C25H33NO11 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: pyridine 2: sodium hydrogencarbonate / N,N-dimethyl-formamide; water 3: pyridine; dmap
  • 71
  • [ 1263291-41-3 ]
  • C17H25NO7 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: pyridine 2: sodium hydrogencarbonate / N,N-dimethyl-formamide; water
  • 72
  • [ 1263291-41-3 ]
  • 4-(4-azidophenyl)-6-phenylpyrimidine-2,5-diamine [ No CAS ]
  • ((5aR,6S,6aS)-1-(4-(2,5-diamino-6-phenylpyrimidin-4-yl)phenyl)-1,4,5,5a,6,6a,7,8-octahydrocyclopropa[5,6]cycloocta[1,2-d][1,2,3]triazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
61% In tetrahydrofuran at 20℃; for 8h; Inert atmosphere;
  • 73
  • [ 1263291-41-3 ]
  • [ 97369-64-7 ]
  • C24H29N2O3(1+)*I(1-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
In acetonitrile at 25℃;
  • 74
  • [ 1263291-41-3 ]
  • [ 20147-41-5 ]
  • C22H24N2O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In acetonitrile at 25℃;
  • 75
  • [ 1263291-41-3 ]
  • C13H13N2O(1+)*I(1-) [ No CAS ]
  • C23H27N2O2(1+)*I(1-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
In acetonitrile at 25℃;
  • 76
  • [ 1263291-41-3 ]
  • C14H12N3O(1+)*I(1-) [ No CAS ]
  • C24H26N3O2(1+)*I(1-) [ No CAS ]
YieldReaction ConditionsOperation in experiment
In acetonitrile at 25℃;
  • 77
  • [ 1263291-41-3 ]
  • [ 201024-81-9 ]
  • C23H25NO2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
In acetonitrile at 25℃;
  • 78
  • [ 1263291-41-3 ]
  • [ 22820-83-3 ]
  • 1,5-ditosyl-7,8-didehydro-2,3,4,5,6,9-hexahydro-1H-1,5-diazonine [ No CAS ]
  • 2,3,5-trichloro-4-(4-(1-(3-azidoadamantane-1-carboxamido)-3-azidomethylbenzene-5-carbonyl)piperazin-1-yl)thiophene S,S-dioxide [ No CAS ]
  • C74H78Cl3N11O7S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% Stage #1: 5,6-didehydro-11,12-dihydrodibenzo[a,e]cyclooctene; 2,3,5-trichloro-4-(4-(1-(3-azidoadamantane-1-carboxamido)-3-azidomethylbenzene-5-carbonyl)piperazin-1-yl)thiophene S,S-dioxide In dichloromethane at 20℃; for 24h; Inert atmosphere; Stage #2: 1,5-ditosyl-7,8-didehydro-2,3,4,5,6,9-hexahydro-1H-1,5-diazonine In dichloromethane at 40℃; Inert atmosphere; Stage #3: (1α,8α,9α)-bicyclo[6.1.0]non-4-yn-9-ylmethanol In dichloromethane at 20℃; for 24h; Inert atmosphere;
  • 79
  • [ 1263291-41-3 ]
  • C64H64Cl3N11O8S3 [ No CAS ]
  • C74H78Cl3N11O7S2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
92% In dichloromethane at 20℃; for 24h; Inert atmosphere;
  • 80
  • [ 14104-20-2 ]
  • [ 1263291-41-3 ]
  • C10H14AgO [ No CAS ]
YieldReaction ConditionsOperation in experiment
In dichloromethane at 20℃; for 1h; Inert atmosphere;
  • 81
  • [ 1263291-41-3 ]
  • [ 82937-45-9 ]
  • rac-((5aS,6R,6aR)-2-(tert-butyl)-3-phenyl-3,4,5,5a,6,6a,7,8-octahydro-2H-cyclopropa[5,6]cycloocta[1,2-d]isoxazol-6-yl)methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
93% In chloroform-d1 at 20℃; for 25h; Inert atmosphere;
  • 82
  • gold(I) tetrafluoroborate [ No CAS ]
  • [ 1263291-41-3 ]
  • C10H14AuO [ No CAS ]
YieldReaction ConditionsOperation in experiment
In dichloromethane at 20℃; for 1h; Inert atmosphere;
  • 83
  • C10H14AgO [ No CAS ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
93% With SiliaMetS-thiourea In dichloromethane at 20℃; for 24h; Inert atmosphere;
  • 84
  • C10H14AuO [ No CAS ]
  • [ 1263291-41-3 ]
YieldReaction ConditionsOperation in experiment
93% With SiliaMetS-thiourea In dichloromethane at 20℃; for 24h; Inert atmosphere;
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