Asymmetric addition of alkylzinc reagents to cyclic alpha,beta-unsaturated ketones and a tandem enantioselective addition/diastereoselective epoxidation with dioxygen.
Although over 100 catalysts have been reported to catalyze the asymmetric addition of alkyl groups to aldehydes, these catalysts fail to promote additions to ketones with >90% enantioselectivity. This paper describes the asymmetric 1,2-addition of alkyl groups to conjugated cyclic enones to give allylic alcohols with chiral quaternary centers. The resultant allylic alcohols are converted into epoxy alcohols with excellent diastereoselectivities. Treatment of the epoxy alcohols with BF3.OEt2 induces a semipinacol rearrangement to provide alpha,alpha-dialkyl-beta-hydroxy ketones with all-carbon chiral quaternary centers. We also report a one-pot procedure for the asymmetric addition/diastereoselective epoxidation reaction. Simply exposing the reaction mixture to dioxygen after the asymmetric addition reaction is complete results in epoxidation of the allylic alcohol with high diastereoselectivity.
Jeon
Sang-Jin
SJ
P. Roy and Diane T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
Walsh
Patrick J
PJ
D000475:Alkenes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D006844:Hydrocarbons, Cyclic / Q000138:chemical synthesis / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D013237:Stereoisomerism; D015032:Zinc / Q000737:chemistry*
D000475:Alkenes; D004852:Epoxy Compounds; D006844:Hydrocarbons, Cyclic; D007659:Ketones; D009942:Organometallic Compounds; D015032:Zinc; D010100:Oxygen