2-Nitrophenyl selenocyanate → rel-(3S,5S)-trans-7-Chloro-5-(2-cyclopropylethenyl)-1,5-dihydro-3-ethenyl-5-(trifluoromethyl)-4,1-benzoxazepin-2(3H)-one

HRID 369750Notes

Reaction equation

HRID 369750 reaction equation
[N+](C1C=CC=CC=1[Se]C#N)([O-])=O.[Na].Br[CH2:15][CH2:16][C@@H:17]1[O:23][C@:22](/[CH:28]=[CH:29]/[CH:30]2[CH2:32][CH2:31]2)([C:24]([F:27])([F:26])[F:25])[C:21]2[CH:33]=[C:34]([Cl:37])[CH:35]=[CH:36][C:20]=2[NH:19][C:18]1=[O:38]>C1COCC1.C(O)C>[Cl:37][C:34]1[CH:35]=[CH:36][C:20]2[NH:19][C:18](=[O:38])[C@H:17]([CH:16]=[CH2:15])[O:23][C@:22](/[CH:28]=[CH:29]/[CH:30]3[CH2:32][CH2:31]3)([C:24]([F:25])([F:26])[F:27])[C:21]=2[CH:33]=1

Participants

6

Reactant 3

HCID 1039312-Nitrophenyl selenocyanateHCID 5360545SodiumHCID 86755964rel-(3S,5S)-trans-3-(2-Bromoethyl)-7-chloro-5-cyclopropylethenyl-1,5-dihydro-5-(trifluoromethyl)-4,1-benzoxazepin-2 (3H)-one

Product 1

HCID 66923228rel-(3S,5S)-trans-7-Chloro-5-(2-cyclopropylethenyl)-1,5-dihydro-3-ethenyl-5-(trifluoromethyl)-4,1-benzoxazepin-2(3H)-oneYield 58.5%

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 8028TetrahydrofuranSolvent2×

Procedure

To a room temperature solution of 238 mg (1.05 mmol) of 2-nitrophenylselenocyanate in 3.0 mL of THF was added 9 mL of ethanol and 66 mg of sodium borchydride. After stirring 1.5 h, a solution of 153 mg of rel-(3S,5S)-trans-3-(2-bromoethyl)-7-chloro-5-cyclopropylethenyl-1,5-dihydro-5-(trifluoromethyl)-4,1-benzoxazepin-2(3H)-one in 1.5 mL of dry THF and 5 mL of ethanol was added, and the resulting mixture was stirred at ambient temperature for 32 h. The reaction mixture was partitioned between water and ether, and the organic layer was washed with aqueous bicarbonate and brine, dried and evaporated. The crude product was purified by column chromatography over silica gel (elution with 10-25% ethyl acetate in hexanes) to give 73 mg of the title compound as a pure solid which can be recrystallized from ethanol-hexanes: mp 165.5-166.5°; HRMS Calcd. for C17H16NO2F3Cl (M+H)+ : 358.082166. Found: 358.081658.

Workup

  1. stirringthe resulting mixture was stirred at ambient temperature for 32 h
  2. customThe reaction mixture was partitioned between water and ether
  3. washthe organic layer was washed with aqueous bicarbonate and brine
  4. customdried
  5. customevaporated
  6. customThe crude product was purified by column chromatography over silica gel (elution with 10-25% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-1968773e180641519c140450cf99f295
Source dataset
uspto-grants-2000_10
Patent number
US06140320

Reaction notes

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