Extending the Aminocatalytic HOMO-Raising Activation Strategy: Where Is the Limit?

Authors


  • Financial support from the Institute of Chemical Research of Catalonia (ICIQ) Foundation and the European Research Council (ERC Starting grant agreement no. 278541—ORGA-NAUT) is gratefully acknowledged.

Abstract

original image

Increasingly remote stereocenters are being targeted in asymmetric aminocatalysis. Application of the HOMO-raising activation concept to δ,δ-disubstituted 2,4-dienones confirms the powerful potential of the trienamine strategy. A cinchona-based primary amine catalyst enables the extension of this activation mode to a highly selective asymmetric Diels–Alder reaction of enones with electron-deficient dienophiles (see scheme; TFA: trifluoroacetic acid).

Ancillary