Iron‐Catalyzed Stereoconvergent 1,4‐Hydrosilylation of Conjugated Dienes

Author:

Sun Wei1,Hu Meng‐Yang1,Lu Zhan‐Sheng1,Huang Ming‐Yao1,Zhang Xin‐Yu1,Zhu Shou‐Fei1ORCID

Affiliation:

1. Frontiers Science Center for New Organic Matter State Key Laboratory and Institute of Elemento-Organic Chemistry College of Chemistry Nankai University Tianjin 300071 China

Abstract

AbstractStereoconvergent transformation of E/Z mixtures of olefins to products with a single steric configuration is of great practical importance but hard to achieve. Herein, we report an iron‐catalyzed stereoconvergent 1,4‐hydrosilylation reactions of E/Z mixtures of readily available conjugated dienes for the synthesis of Z‐allylsilanes with high regioselectivity and exclusive stereoselectivity. Mechanistic studies suggest that the reactions most likely proceed through a two‐electron redox mechanism. The stereoselectivity of the reactions is ultimately determined by the crowded reaction cavity of the α‐diimine ligand‐modified iron catalyst, which forces the conjugated diene to coordinate with the iron center in a cis conformation, which in turn results in generation of an anti‐π‐allyl iron intermediate. The mechanism of this stereoconvergent transformation differs from previously reported mechanisms of other related reactions involving radicals or metal‐hydride species.

Funder

National Key Research and Development Program of China

National Natural Science Foundation of China

Ministry of Education of the People's Republic of China

Fundamental Research Funds for Central Universities of the Central South University

Publisher

Wiley

Subject

General Medicine

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3. C. R. Larsen D. B. Grotjahn inApplied Homogeneous Catalysis with Organometallic Compounds: A Comprehensive Handbook Vol. 4(Eds.: B. Cornils W. A. Herrmann M. Beller R. Paciello) Wiley Hoboken 2017 pp. 1365–1378.

4. H. U. Blaser H. J. Federsel Asymmetric Catalysis on Industrial Scale Wiley-VCH Weinheim 2010 pp.187–205.

5. M. Porterin Modern Carbonyl Olefination: Methods and Applications(Eds.: T. Takeda) Wiley-VCH Weinhem 2004.

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