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Author Notes:

Corresponding authors: Djamaladdin G. Musaev, Cherry L. Emerson Center for Scientific Computation, Emory University, 1521 Dickey Drive, Atlanta, GA 30322, USA; Email: dmusaev@emory.edu

Huw M. L. Davies, Department of Chemistry, Emory University, 1515 Dickey Drive, Atlanta, GA 30322, USA; Fax: 404-727-7766; Telephone: 404-727-6839; Email: hmdavie@emory.edu

We thank Dr. John Bacsa, Emory University, for the X-ray crystallographic analysis.

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Research Funding:

The synthetic studies were supported by the National Institute of Health (GM-099142-01).

The computational studies were supported by NSF under the CCI Center for Selective C–H Functionalization, CHE-1205646.

The authors gratefully acknowledge NSF MRI-R2 grant (CHE-0958205) and the use of the resources of the Cherry Emerson Center for Scientific Computation.

Rhodium-catalyzed enantioselective cyclopropanation of electron deficient alkenes

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Journal Title:

Chemical Science

Volume:

Volume 4, Number 7

Publisher:

, Pages 2844-2850

Type of Work:

Article | Post-print: After Peer Review

Abstract:

The rhodium-catalyzed reaction of electron-deficient alkenes with substituted aryldiazoacetates and vinyldiazoacetates results in highly stereoselective cyclopropanations. With adamantylglycine derived catalyst Rh2(S-TCPTAD)4, high asymmetric induction (up to 98% ee) can be obtained with a range of substrates. Computational studies suggest that the reaction is facilitated by weak interaction between the carbenoid and the substrate carbonyl but subsequently proceeds via different pathways depending on the nature of the carbonyl. Acrylates and acrylamides result in the formation of cyclopropanation products while the use of unsaturated aldehydes and ketones results in the formation of epoxides.

Copyright information:

© The Royal Society of Chemistry 2013

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