Financial support by the Deutsche Forschungsgemeinschaft, and generous allotment of computational time from the Research Center for Computational Science, National Institutes of Natural Sciences (Japan), the National Center for Supercomputing Applications (University of Illinois at Urbana-Champaign, USA), and the Cherry L. Emerson Center for Scientific Computation (Emory University, Atlanta, U.S.A.) are gratefully acknowledged.
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Communication
Elucidation of the Mechanism of the 1,6-Cuprate Addition to Acceptor-Substituted Enynes through 13C Kinetic Isotope Effects: Experimental and Theoretical Studies†
Article first published online: 1 JUL 2005
DOI: 10.1002/anie.200462976
Copyright © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Additional Information
How to Cite
Mori, S., Uerdingen, M., Krause, N. and Morokuma, K. (2005), Elucidation of the Mechanism of the 1,6-Cuprate Addition to Acceptor-Substituted Enynes through 13C Kinetic Isotope Effects: Experimental and Theoretical Studies. Angewandte Chemie International Edition, 44: 4715–4719. doi: 10.1002/anie.200462976
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Publication History
- Issue published online: 18 JUL 2005
- Article first published online: 1 JUL 2005
- Manuscript Revised: 5 APR 2005
- Manuscript Received: 17 DEC 2004
Keywords:
- allenes;
- cuprates;
- density functional calculations;
- isotope effects;
- Michael addition
Graphical Abstract
A combination of experimental and theoretical studies of 13C kinetic isotope effects have led to a comprehensive mechanistic picture of the 1,6-cuprate addition to acceptor-substituted enynes. In the rate-determining step, the new bond is formed from the triple bond of the substrate to the incoming alkyl group (see scheme).