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Synthesis 2017; 49(19): 4448-4460
DOI: 10.1055/s-0036-1590873
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© Georg Thieme Verlag Stuttgart · New York

Asymmetric Desymmetrization of Substituted Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation and Theoretical Calculations of Its Mechanistic Aspects

Yuki Naganawa*
a   Interdisciplinary Research Center for Catalytic Chemistry (IRC3), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8565, Japan   Email: yuki.naganawa@aist.go.jp
,
Jun-ichi Ito
b   Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan   Email: hnishi@apchem.nagoya-u.ac.jp
,
Mayu Kawagishi
b   Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan   Email: hnishi@apchem.nagoya-u.ac.jp
,
Hisao Nishiyama*
b   Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan   Email: hnishi@apchem.nagoya-u.ac.jp
› Author AffiliationsThis research was supported by Grants-in-Aid for Scientific Research from the Japan Society for the Promotion of Science (Nos. 15H03808 and 15K21063).
Further Information

Publication History

Received: 08 June 2017

Accepted after revision: 19 July 2017

Publication Date:
15 August 2017 (online)

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Abstract

Asymmetric desymmetrization was demonstrated by means of transition-metal-catalyzed conjugate reduction with hydrosilanes as reductants. Chiral rhodium-bis(oxazolinyl)phenyl complexes [Rh(Phebox-R)] were found to be effective catalysts for conjugate hydrosilylation of differently γ,γ-disubstituted cyclohexadienones to provide the corresponding product with chiral quaternary centers. The mechanistic consideration was also performed by theoretical calculation. These attempts provided information about i) the initial activation of Rh(III) complex into Rh(I) species assisted by hydrosilanes, ii) the complete catalytic cycle, and iii) an explanation of the asymmetric induction and the difference of the structure of cyclohexadienones in enantioselectivity.

Key words

asymmetric synthesis - desymmetrization - quaternary center - rhodium - hydrosilane - conjugate reduction - computational study

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590873.
  • Supporting Information
 

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