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 Jan 2012
Accepted
18 Apr 2012
First published
19 Apr 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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements