Issue 30, 2012

Desymmetrizing reductive aldol cyclizations of enethioate derivatives of 1,3-diones catalyzed by a chiral copper hydride

Abstract

A range of enethioate derivatives of 1,3-diones underwent reductive aldol cyclizations catalyzed by a chiral copper hydride generated in situ from 5 mol% TaniaPhos (SL-T001-1), 5 mol% Cu(OAc)2·H2O, 5 mol% bipyridine and 2.0 equiv. of PhSiH3, to furnish polycyclic β-hydroxythioester products bearing three newly established contiguous stereocenters, with >98 : 2 dr and in up to 94% yield and 98% ee. The use of an amine such as bipyridine or 2,6-lutidine as additive results in an increase of the overall reaction rate. The major bicyclic aldol product has all substituents cis and can be rationalized by a reductively generated (Z)-enolate reacting with the dione via a cyclic transition state.

Graphical abstract: Desymmetrizing reductive aldol cyclizations of enethioate derivatives of 1,3-diones catalyzed by a chiral copper hydride

Supplementary files

Article information

Article type
Paper
Submitted
27 1 2012
Accepted
18 4 2012
First published
19 4 2012

Org. Biomol. Chem., 2012,10, 5971-5978

Desymmetrizing reductive aldol cyclizations of enethioate derivatives of 1,3-diones catalyzed by a chiral copper hydride

J. Ou, W. Wong and P. Chiu, Org. Biomol. Chem., 2012, 10, 5971 DOI: 10.1039/C2OB25206F

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