Asymmetric Induction at Remote Quaternary Centers of Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation

Yuki Naganawa; Mayu Kawagishi; Jun-Ichi Ito; Hisao Nishiyama

doi:10.1002/anie.201601636

Asymmetric Induction at Remote Quaternary Centers of Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation

Angew Chem Int Ed Engl. 2016 Jun 6;55(24):6873-6. doi: 10.1002/anie.201601636. Epub 2016 Apr 21.

Authors

Yuki Naganawa¹, Mayu Kawagishi², Jun-Ichi Ito², Hisao Nishiyama³

Affiliations

¹ Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya, 464-8603, Japan. yuki.n@apchem.nagoya-u.ac.jp.
² Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya, 464-8603, Japan.
³ Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya, 464-8603, Japan. hnishi@apchem.nagoya-u.ac.jp.

PMID: 27100774
DOI: 10.1002/anie.201601636

Abstract

The enantioselective desymmetrizing conjugate hydrosilylation of prochiral differently γ,γ-disubstituted cyclohexadienone derivatives 2 to furnish the corresponding cyclohexenones 4 with a remote chiral all-carbon quaternary center at the γ position is described. Chiral rhodium-bis(oxazolinyl)phenyl complexes 1 were effective catalysts for this transformation. This catalytic system was extended to the asymmetric transformation of spirocarbocyclic cyclohexadienones 5 to give the corresponding products 6 with high enantiomeric ratios.

Keywords: asymmetric synthesis; desymmetrization; hydrosilylation; quaternary centers; rhodium.

Publication types

Research Support, Non-U.S. Gov't