2-Nitrophenyl selenocyanate → rel-(3S,5S)-7-Chloro-5-(2-cyclopropylethynyl)-1,5-dihydro-3-ethen yl-5-(trifluoromethyl)-4,1-benzoxazepin-2(3H)-one

HRID 369748Notes

Reaction equation

HRID 369748 reaction equation
[N+](C1C=CC=CC=1[Se]C#N)([O-])=O.[BH4-].[Na+].Br[CH2:16][CH2:17][CH:18]1[O:24][C:23]([C:29]#[C:30][CH:31]2[CH2:33][CH2:32]2)([C:25]([F:28])([F:27])[F:26])[C:22]2[CH:34]=[C:35]([Cl:38])[CH:36]=[CH:37][C:21]=2[NH:20][C:19]1=[O:39]>C1COCC1.C(O)C>[Cl:38][C:35]1[CH:36]=[CH:37][C:21]2[NH:20][C:19](=[O:39])[C@H:18]([CH:17]=[CH2:16])[O:24][C@:23]([C:29]#[C:30][CH:31]3[CH2:33][CH2:32]3)([C:25]([F:26])([F:27])[F:28])[C:22]=2[CH:34]=1

Participants

6

Reactant 3

HCID 1039312-Nitrophenyl selenocyanateHCID 4311764Sodium borohydride2×HCID 183873743-(2-Bromoethyl)-7-chloro-5-cyclopropylethynyl-1,5-dihydro-5-(trifluoromethyl)-4,1-benzoxazepin-2(3H)-one

Product 1

HCID 56994752rel-(3S,5S)-7-Chloro-5-(2-cyclopropylethynyl)-1,5-dihydro-3-ethen yl-5-(trifluoromethyl)-4,1-benzoxazepin-2(3H)-one

Reagents, catalysts & solvents 2

HCID 702EthanolSolvent2×HCID 8028TetrahydrofuranSolvent2×

Procedure

To a room temperature solution of 409 mg (1.8 mmol) of 2-nitrophenylselenocyanate in 5.0 mL of THF was added 16 mL of ethanol and 90 mg of sodium borohydride. After stirring 1 h, a solution of 260 mg of rel-3S,5S)-3-(2-Bromoethyl)-7-chloro-5-cyclopropylethynyl-1,5-dihydro-5-(trifluoromethyl)-4,1-benzoxazepin-2(3H)-one in 1.5 mL of dry THF and 8 mL of ethanol was added, and the resulting mixture was stirred at ambient temperature for 2 h, at which time an additional 20 mg of sodium borohydride was added and stirring was continued for an additional 2 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 130 mg of the title compound as a pure solid: HRMS: Calcd. for C17H14NO2F3Cl (M+H)+ : 354.0508. Found: 354.0487.

Workup

  1. additionwas added
  2. stirringstirring
  3. waitwas continued for an additional 2 h
  4. customThe reaction mixture was partitioned between water and ether
  5. washthe organic layer was washed with aqueous bicarbonate and brine
  6. customdried
  7. customevaporated
  8. customThe crude product was purified by column chromatography over silica gel (elution with 10-25% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-3b92645894154340bb2677abb054b1b4
Source dataset
uspto-grants-2000_10
Patent number
US06140320

Reaction notes

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