Ethyl formate → HCID 86718468, compound

HRID 1396649Notes

Reaction equation

HRID 1396649 reaction equation
[CH3:1][S:2]([CH3:15])(=[N:4][C:5]([O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:6])=[O:3].[Li+].C[Si]([N-][Si](C)(C)C)(C)C.C(O[CH2:29][CH3:30])=O.[NH:31]1[CH2:35]C[CH2:33][CH2:32]1.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>C1COCC1.O.CCOC(C)=O>[CH3:1][S:2](=[O:3])([CH2:15][CH2:35][N:31]1[CH2:30][CH2:29][CH2:33][CH2:32]1)=[N:4][C:5](=[O:6])[O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

9

Reactant 5

HCID 8025Ethyl formateHCID 31268PyrrolidineHCID 2733832Lithium HexamethyldisilazideHCID 5049666Sodium triacetoxyborohydrideHCID 85891357HCID 85891357, compound

Product 1

HCID 86718468HCID 86718468, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent4×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

A mixture of 0.5 g (2.2 mmol) S,S-Dimethyl-N-[(phenylmethoxy)-carbonyl]sulfoximine (J. Org. Chem., 2005, 70 (23), 9599) and THF is cooled to −78° C. and 2.3 ml (2.3 mmol) LiHMDS 1M in THF is added dropwise and the mixture is stirred for 20 minutes. 0.2 g (2.3 mmol) Ethyl formate in THF is added and the mixture is stirred at −78° C. for 50 minutes warmed to RT and stirred for additional 4 h. The Reaction mixture is diluted with water and EtOAc, the aqueous phase is separated and extracted with EtOAc. The organic phases are pooled and washed with water and brine, dried and evaporated. To a mixtue of the residual, 0.1 g (1.6 mmol) pyrrolidine and THF 0.1 g acetic acid and 0.4 g (2.0 mmol) NaBH(OAc)3 are added and the reaction mixture is stirred at RT over night. The reaction mixture is evaporated and purified by HPLC giving rise to benzyl N—[methyl-oxo-(2-pyrrolidin-1-ylethyl)-λ6-sulfanylidene]carbamate.

Workup

  1. stirringthe mixture is stirred at −78° C. for 50 minutes
  2. temperaturewarmed to RT
  3. stirringstirred for additional 4 h
  4. customthe aqueous phase is separated
  5. extractionextracted with EtOAc
  6. washwashed with water and brine
  7. customdried
  8. customevaporated
  9. stirringthe reaction mixture is stirred at RT over night
  10. customThe reaction mixture is evaporated
  11. custompurified by HPLC

Sources & evidence

ORD record
ord-62e52617fb7c4bc9be9bd7af9dd68a9d
Source dataset
uspto-grants-2014_12
Patent number
US08901138B2

Reaction notes

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