Ethyl chloroformate → Allyl chloroformate

HRID 2061385Notes

Reaction equation

HRID 2061385 reaction equation
[Cl:1][C:2]([O:4][CH2:5][CH3:6])=[O:3].[CH:7]([N:10]([CH:13]([CH3:15])[CH3:14])[CH2:11][CH3:12])([CH3:9])[CH3:8]>>[Cl:1][C:2]([O:4][CH2:5][CH:6]=[CH2:7])=[O:3].[CH:7]([N:10]([CH:13]([CH3:15])[CH3:14])[CH2:11][CH3:12])([CH3:9])[CH3:8]

Participants

4

Reactant 2

HCID 10928Ethyl chloroformateHCID 81531Diisopropylethylamine

Product 2

HCID 18052Allyl chloroformateHCID 81531Diisopropylethylamine

Procedure

In Scheme 2, 2-bromobenzenesulfonyl chloride (25) and 2-phenyl allyl amine (33) are reacted in the presence of pyridine to generate intermediate (34) which, upon treatment with TBTH and AIBN in toluene gives the radical derived adduct (35) which, when reacted with (2S,3S)-1,2-epoxy-3-(boc-amino)-4-phenylbutane (29) in the presence of Cs2CO3 gives compound (36), as mixture of two diastereomers. The mixture of two diastereomers is treated with TFA:DCM (1:1) to produce compound (37) as a mixture of diastereomers. Treatment of (37) with substituted chloroformates for example ethyl chloroformate in the presence of di-isopropyl-N-ethylamine yielded a mixture of diastereomers which could be separated into pure diastereomers (10) and (11) using preparative TLC. Similarly, compound (37) on treatment with allyl chloroformate in the presence of di-isopropyl-N-ethylamine yielded a mixture of diastereomers which could be separated by preparative TLC into pure diastereomers (8) and (9).

Workup

  1. additionas a mixture of diastereomers
  2. additiona mixture of diastereomers which
  3. customcould be separated into pure diastereomers (10) and (11)

Sources & evidence

ORD record
ord-08d5413637f7488db247232967e31e41
Source dataset
uspto-grants-2012_10
Patent number
US08283346B2

Reaction notes

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