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Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions

Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions

Published on: July 17, 2020

Catalytic Enantioselective Formal (4+2) Cycloaddition by Aldol-Aldol Annulation of Pyruvate Derivatives with

Pandurang V Chouthaiwale¹, Ravindra D Aher¹, Fujie Tanaka¹

¹Chemistry and Chemical Bioengineering Unit, Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna, Okinawa, 904-0495, Japan.

Angewandte Chemie (International Ed. in English)

|August 21, 2018

Abstract:

The decalin structure is found in bioactive molecules. We have developed catalytic enantioselective formal (4+2) cycloaddition reactions via aldol-aldol cascade reactions between pyruvate-derived diketoester derivatives and cyclohexane-1,3-dione derivatives that afford highly functionalized decalin derivatives. The reactions were performed using a quinidine-derived catalyst under mild conditions. Decalin derivatives bearing up to six chiral carbon centers including tetrasubstituted carbon centers were synthesized with high diastereo- and enantioselectivities. Five to six stereogenic centers were generated from achiral molecules with the formation of two C-C bonds in a single transformation resulting in the formation of the decalin system.

Keywords:

aldol reactions asymmetric catalysis asymmetric synthesis organocatalysis

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