Triisopropyl phosphite → HCID 54076213, compound

HRID 376173Notes

Reaction equation

[C:1]([O:4][CH2:5][CH2:6][C:7]([CH2:18]Br)=[CH:8][C@@H:9]([NH:15][CH:16]=[O:17])[C:10]([O:12][CH2:13][CH3:14])=[O:11])(=[O:3])[CH3:2].[P:20]([O:29]C(C)C)([O:25][CH:26]([CH3:28])[CH3:27])[O:21][CH:22]([CH3:24])[CH3:23]>>[C:1]([O:4][CH2:5][CH2:6][C:7]([CH2:18][P:20]([O:25][CH:26]([CH3:28])[CH3:27])([O:21][CH:22]([CH3:24])[CH3:23])=[O:29])=[CH:8][C@@H:9]([NH:15][CH:16]=[O:17])[C:10]([O:12][CH2:13][CH3:14])=[O:11])(=[O:3])[CH3:2]

Participants

Reactant 2

HCID 8304Triisopropyl phosphite

HCID 54470495HCID 54470495, compound

Product 1

HCID 54076213HCID 54076213, compoundYield 32.3%

Procedure

21.2 g (63.1 mmol) of ethyl 6-acetoxy-4-bromomethyl-2(R)-formylamino-hex-3-enoate and 69.1 ml (252.2 mmol) of 90% triisopropyl phosphite are heated to 80° C. and the mixture is stirred for 18 hours under a pressure of 100-150 mbar. Excess triisopropyl phosphite is removed by distillation and the residue is purified by flash chromatography on silica gel with ethyl acetate/ethanol (19:1), giving 8.6 g of ethyl 6-acetoxy-2(R)-formylamino-4-diisopropylphosphonomethyl-hex-3-enoate a yellowish-orange oil. ee=92.5%; αD -90.2°±0.4°, (c=2.84 CH2Cl2).

Workup

customExcess triisopropyl phosphite is removed by distillation
customthe residue is purified by flash chromatography on silica gel with ethyl acetate/ethanol (19:1)

Sources & evidence

ORD record: ord-92f4182231a04d68987188f6964f74bf
Source dataset: uspto-grants-1996_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05488140

Reaction notes

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