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

Jun Ou, Wing Tak Wong, Pauline Chiu

Research output: Journal article publicationJournal articleAcademic researchpeer-review

31 Citations (Scopus)

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.
Original languageEnglish
Pages (from-to)5971-5978
Number of pages8
JournalOrganic and Biomolecular Chemistry
Volume10
Issue number30
DOIs
Publication statusPublished - 14 Aug 2012
Externally publishedYes

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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