N-boranyl-2-methylpropan-2-amine → 6-Bromo-2-(1-phenyl-ethyl)-1,2,3,3a,7,7a-hexahydro-4-thia-2-aza-cyclopenta[alpha]pentalene

HRID 30293Notes

Reaction equation

HRID 30293 reaction equation
C(NB)(C)(C)C.[Al+3].[Cl-].[Cl-].[Cl-].[Br:11][C:12]1[C:16]2[C:17](=O)[CH:18]3[CH:22]([C:15]=2[S:14][CH:13]=1)[CH2:21][N:20]([CH:23]([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[CH3:24])[CH2:19]3.B.[Al+3].[Cl-].[Cl-].[Cl-]>ClCCl>[Br:11][C:12]1[C:16]2[CH2:17][CH:18]3[CH:22]([C:15]=2[S:14][CH:13]=1)[CH2:21][N:20]([CH:23]([C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)[CH3:24])[CH2:19]3

Participants

6

Reactant 4

HCID 3639180N-boranyl-2-methylpropan-2-amineHCID 6451240Aluminum(III) ChlorideHCID 1317270486-Bromo-2-(1-phenyl-ethyl)-2,3,3a,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalen-7-oneHCID 178419134HCID 178419134, compound

Product 1

HCID 1317270476-Bromo-2-(1-phenyl-ethyl)-1,2,3,3a,7,7a-hexahydro-4-thia-2-aza-cyclopenta[alpha]pentaleneYield 74.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

t-Butylaminoborane (1080 mg, 12.42 mmol) was added to a suspension of AlCl3 (828 mg, 6.21 mmol) in 30 mL of dichloromethane at 0° C. and the reaction mixture was allowed to come to room temperature and stirred for 30 minutes. The product from step e) (746 mg, 2.07 mmol) dissolved in 10 mL dichloromethane was added to the borane/AlCl3 reaction mixture and stirred at room temperature for 12 hours. The reaction was quenched with 2 N NaOH to pH=12. The organic phase was separated washed with brine and dried with MgSO4. The solvent was evaporated leaving a white solid. The crude was purified by column chromatography (SiO2) using 5-50% ethylacetate-hexane gradient to afford the subtitle compound (536 mg, yield: 74.6%). MS calculated for C17H18BrNS+H: 348, observed: 348 and 350.

Workup

  1. customto come to room temperature
  2. stirringstirred at room temperature for 12 hours
  3. customThe reaction was quenched with 2 N NaOH to pH=12
  4. customThe organic phase was separated
  5. washwashed with brine
  6. dry with materialdried with MgSO4
  7. customThe solvent was evaporated
  8. customleaving a white solid
  9. customThe crude was purified by column chromatography (SiO2)

Sources & evidence

ORD record
ord-027748b5f12b47de8046d261e142a6eb
Source dataset
uspto-grants-2008_09
Patent number
US07423056B2

Reaction notes

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