Enantioselective, organocatalytic oxy-michael addition to gamma/delta-hydroxy-alpha,beta-enones: boronate-amine complexes as chiral hydroxide synthons.

ABSTRACT: An organocatalytic, enantioselective oxy-Michael addition to achiral gamma- and delta-hydroxy-alpha,beta-enones was developed. The key transformation is an unprecedented, asymmetric conjugate addition triggered by complexation between an in situ generated boronic acid hemiester and a chiral amine catalyst. Functionally, the intermediate amine-boronate complex acts as a chiral hydroxide surrogate or synthon. The resultant chiral beta-hydroxy-ketones are obtained in good to excellent yields and high ee following mild oxidative removal of the cyclic boronate. Natural products (R,12Z,15Z)-2-hydroxy-4-oxohenicosa-12,15-dienyl acetate and (+)-(S)-streptenol A were synthesized to demonstrate the utility of this reaction.

SUBMITTER: Li de R 

PROVIDER: S-EPMC2597475 | biostudies-literature | 2008 Jan

REPOSITORIES: biostudies-literature