Jump to main content
Jump to site search

Issue 30, 2012
Previous Article Next Article

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

Author affiliations

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 27 Jan 2012, accepted on 18 Apr 2012 and first published on 19 Apr 2012


Article type: Paper
DOI: 10.1039/C2OB25206F
Citation: Org. Biomol. Chem., 2012,10, 5971-5978
  •   Request permissions

    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

Search articles by author

Spotlight

Advertisements