Evidence for an enolate mechanism in the asymmetric Michael reaction of α,β-unsaturated aldehydes and ketones via a hybrid system of two secondary amine catalysts

Author:

Umekubo Nariyoshi12345,Terunuma Takahiro12345,Kwon Eunsang62345,Hayashi Yujiro12345ORCID

Affiliation:

1. Department of Chemistry

2. Graduate School of Science

3. Tohoku University

4. Sendai 980-8578

5. Japan

6. Research and Analytical Center for Giant Molecules

Abstract

The key nucleophile was found to be neither an enamine nor an enol, but an enolate in the direct Michael reaction of α,β-unsaturated aldehydes and non-activated ketones catalyzed by two amine catalysts namely diphenylprolinol silyl ether and pyrrolidine.

Funder

Japan Society for the Promotion of Science

Publisher

Royal Society of Chemistry (RSC)

Subject

General Chemistry

Reference57 articles.

1. H. B. Mekelburger and C. S.Wilcox , Comprehensive Organic Synthesis , Elsevier , Amsterdam , 2nd edn, 2014 , vol. 2 , pp. 243–272

2. B. M. Stoltz , N. B.Bennett , D. C.Duquette , A. F. G.Goldberg , Y.Liu , M. B.Loewinger and C. M.Reeves , Comprehensive Organic Synthesis , Elsevier , Amsterdam , 2nd edn, 2014 , vol. 3 , pp. 1–55

3. H. O. House , Modern Synthetic Reactions , 2nd edn, Benjamin , Philippines , 1972 , p. 492

4. While the p K a of cyclohexanone is 26.4 (in DMSO), those of isopropylamine and TMS 2 NH are 36 and 30 (in THF), respectively. Evans' p K a Table can be found in http://evans.rc.fas.harvard.edu/pdf/evans_pKa_table.pdf

5. For representative reviews on organocatalysis, see;

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