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Synthesis 2017; 49(19): 4448-4460
DOI: 10.1055/s-0036-1590873
DOI: 10.1055/s-0036-1590873
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Asymmetric Desymmetrization of Substituted Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation and Theoretical Calculations of Its Mechanistic Aspects
This 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)
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 studySupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590873.
- Supporting Information
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