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

Organic & Biomolecular Chemistry
Jun OuPauline Chiu

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)·H(2)O, 5 mol% bipyridine and 2.0 equiv. of PhSiH(3), 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.

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Citations

Jul 28, 2016·Chemical Reviews·Abraham J JordanJoseph P Sadighi
May 31, 2018·Chemical Society Reviews·Yasuhiro YamashitaShū Kobayashi
Mar 24, 2020·Chemical Communications : Chem Comm·Pan Zhou, Tao Xu
Jan 20, 2016·Chemistry : a European Journal·Kong Ching WongPauline Chiu
Mar 30, 2021·Chemistry : a European Journal·Baptiste LecacheyJean-Marc Campagne
Jul 14, 2021·Organic Letters·Yongjie ShiPauline Chiu

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