Issue 13, 2020

Copper(i)-catalyzed highly enantioselective [3 + 3]-cycloaddition of γ-alkyl enoldiazoacetates with nitrones

Abstract

Chiral copper(I) catalysts are preferred over chiral dirhodium(II) catalysts for [3 + 3]-cycloaddition reactions of γ-alkyl-substituted enoldiazoacetates compounds with nitrones. Using the In-SaBox ligand these reactions effectively produce cis-3,6-dihydro-1,2-oxazine derivatives under mild conditions in high yield and with exceptional stereocontrol, and enantioselectivity increases with the size of the γ-substituent. Mechanistic studies show that cycloaddition occurs solely through the formation of (Z)-γ-substituted metallo-enolcarbene intermediates that are catalytically gennerated from both (Z)- and (E)-γ-substituted enoldiazoactates via donor–acceptor cyclopropene intermediates.

Graphical abstract: Copper(i)-catalyzed highly enantioselective [3 + 3]-cycloaddition of γ-alkyl enoldiazoacetates with nitrones

Supplementary files

Article information

Article type
Research Article
Submitted
04 May 2020
Accepted
27 May 2020
First published
27 May 2020

Org. Chem. Front., 2020,7, 1653-1657

Author version available

Copper(I)-catalyzed highly enantioselective [3 + 3]-cycloaddition of γ-alkyl enoldiazoacetates with nitrones

K. Dong, X. Xu and M. P. Doyle, Org. Chem. Front., 2020, 7, 1653 DOI: 10.1039/D0QO00539H

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