1,4-Chirality transfer via the ester enolate Claisen rearrangements in the preparation of (25R)- and (25S)-cholestenoic acids.

Abstract:

:Two variants of the Claisen rearrangement were evaluated for a stereoselective construction of a C-25 stereogenic center in cholestenoic acids based on 1,4-chirality transfer. Johnson orthoester Claisen rearrangement of (22R)- and (22S)-propargyl enol ethers proceeded in a highly stereoselective manner to give (25R)- and (25S)-isomeric allenes. The stereochemical outcome of the Ireland-Claisen rearrangement of 22-allylic alcohols was dependent on the configuration of the C-22 hydroxyl group and the geometry of the enol ether. The latter could be controlled by the solvent (THF or a mixture of THF/HMPA) chosen for the generation of silyl enolate.

journal_name

Steroids

journal_title

Steroids

authors

Ermolovich YV,Zhabinskii VN,Khripach VA

doi

10.1016/j.steroids.2013.03.006

subject

Has Abstract

pub_date

2013-07-01 00:00:00

pages

683-92

issue

7

eissn

0039-128X

issn

1878-5867

pii

S0039-128X(13)00064-0

journal_volume

78

pub_type

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