DBU-Catalyzed Ring-Opening and Retro-Claisen Fragmentation of Dihydropyranones
Journal article, 2020

We present a general protocol for the formal Michael addition of acetone to alpha,beta-unsaturated esters and amides, a transformation difficult to perform using current methods. The protocol comprises of an amidine catalyzed relay ring-opening and fragmentation of 3,4-dihydropyranones. The reaction proceeds under mild conditions, has a broad substrate scope and the products can be isolated in good to excellent yields. The method can be applied to homochiral substrates with total preservation of chiral information, generating products in high optical purity. Kinetic experiments supported by quantum chemical modeling indicate a mechanism in which the catalyst takes a bifunctional role, acting both as a Bronsted base and as a hydrogen-bond donor.

Organocatalysis

Retro-claisen

Oxygen heterocycles

Synthetic methods

Michael addition

Author

Anton Axelsson

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry, Physical Chemistry

Emmelie Hammarvid

Student at Chalmers

Martin Rahm

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

Henrik Sunden

University of Gothenburg

European Journal of Organic Chemistry

1434-193X (ISSN)

Vol. 2020 33 5436-5444

Subject Categories

Other Chemical Engineering

Biocatalysis and Enzyme Technology

Organic Chemistry

DOI

10.1002/ejoc.202000858

More information

Latest update

10/30/2020