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Stage #1: bromoacetic acid <i>tert</i>-butyl ester; (±)-benzyl 2-cyanopyrrolidine-1-carboxylate With ethylene dibromide; zinc In tetrahydrofuran for 1h; Heating;
Stage #2: With potassium carbonate In tetrahydrofuran; water for 0.25h;
Stage #3: With sodium hydride In tetrahydrofuran at 0 - 20℃; Further stages.;
With hydrogenchloride In diethyl ether at -20℃; for 12h;
89.4
2-Cyano-pyrrolidine-1-carboxylic acid benzyl ester (17.0 g, 73.9 mmol) was dissolved in diethyl ether (100 mL). Ethanol (20.4 g, 444 mmol) was added and gaseous HCl was bubbled through the reaction mixture, while maintaining the temperature at -20° C. The temperature was maintained for 12 hours while stirring. The reaction mixture was concentrated under vacuo to afford 22.0 g (95%) of 2-ethoxycarbonimidoyl-pyrrolidine-1-carboxylic acid benzyl ester as a red oil.
In pyridine; dichloromethane at -10℃; for 2.66667h;
89.3
Carbamoyl-pyrrolidine-1-carboxylic acid benzyl ester (25.0 g, 101 mmol) was dissolved in pyridine (125 mL) under an N2 atmosphere and cooled to -10° C. The phosphorus oxychloride (12.6 mL, 135 mmol) was dissolved in DCM (25 mL) and added dropwise over 40 mins to the pyridine solution. The reaction mixture's temperature was maintained at -10° C. and the solution was allowed to stir for 2 hours. The reaction was quenched by addition of water/ice (100 g) and transferred into a separatory funnel. The solution was extracted with diethyl ether (3×200 mL). The organic layers were combined and washed with saturated cupric sulfate (200 mL). The organic layer was dried over MgSO4 and concentrated under vacuo to afford 20.0 g (82%) of 2-cyano-pyrrolidine-1-carboxylic acid benzyl ester as a green oil.
5-fluoro-1-cyano-1,2-benziodoxol-3-(1H)-one[ No CAS ]
[ 1148-11-4 ]
[ 119020-06-3 ]
Yield
Reaction Conditions
Operation in experiment
75%
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; Irradiation; Molecular sieve;
75%
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; UV-irradiation; Molecular sieve;
5-nitro-1-cyano-1,2-benziodoxol-3-(1H)-one[ No CAS ]
[ 1148-11-4 ]
[ 119020-06-3 ]
Yield
Reaction Conditions
Operation in experiment
44%
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; Irradiation; Molecular sieve;
44%
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; UV-irradiation; Molecular sieve;
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; Irradiation; Molecular sieve;
52%
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; UV-irradiation; Molecular sieve;
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; Irradiation; Molecular sieve;
10%
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; UV-irradiation; Molecular sieve;
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; Irradiation; Molecular sieve;
10%
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; UV-irradiation; Molecular sieve;
With [4,4′-bis(1,1-dimethylethyl)-2,2′-bipyridine-N1,N1′]bis{3,5-difluoro-2-[5-(trifluoromethyl)-2-pyridinyl-κN]phenyl-κC}iridium(III) hexafluorophosphate; cesium benzoate In tetrahydrofuran at 20℃; for 4.5h; UV-irradiation; Molecular sieve;
With [Ir(2-(2,4-difluorophenyl)-4-(trifluoromethyl)pyridine)2(5,5'-bis(trifluoromethyl)-2,2'-bipyridine)]PF6; (S)-1,1'-binaphthyl-2,2'-diyl hydrogen phosphate; potassium carbonate In dichloromethane at 20℃; for 4h; Inert atmosphere; Sealed tube; Irradiation;