This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Advanced Molecular Transformations by Organocatalysts” from The Ministry of Education, Culture, Sports, Science and Technology (Japan). We thank Tsukuba Advanced Computing Center (TACC) in AIST for the provision of the computational facilities.
Organocatalytic 1,4-Addition Reaction of α,β-γ,δ-Diunsaturated Aldehydes versus 1,6-Addition Reaction†
Article first published online: 29 MAY 2012
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Special Issue: Organocatalysis
Volume 4, Issue 7, pages 959–962, July 2012
How to Cite
Hayashi, Y., Okamura, D., Umemiya, S. and Uchimaru, T. (2012), Organocatalytic 1,4-Addition Reaction of α,β-γ,δ-Diunsaturated Aldehydes versus 1,6-Addition Reaction. ChemCatChem, 4: 959–962. doi: 10.1002/cctc.201200161
- Issue published online: 22 JUN 2012
- Article first published online: 29 MAY 2012
- Manuscript Received: 17 MAR 2012
- Grant-in-Aid for Scientific Research
- Ministry of Education, Culture, Sports, Science and Technology
- asymmetric reaction;
- Michael reaction;
Among 1,4-addition and 1,6-addition reactions, 1,4-addition reaction is the main reaction mode in the Michael reaction of α,β-γ,δ-diunsaturated aldehyde with several nucleophiles catalyzed by diphenylprolinol silyl ether via iminium ion intermediate. The 1,4-addition products, which possess excellent enantioselectivity and alkene moiety, are useful chiral building blocks. The ab initio calculation indicates that 1,4-addition reaction is preferable in terms of π-orbital coefficient and Mulliken/CHelpG atomic charge.