Diastereoselective reactions of delta-oxy-substituted allylic acetates with organocopper reagents.
S(N)2' (gamma) substitutions of delta-substituted allylic acetates with Grignard reagents and copper catalysts proceed with high diastereoselectivities. With benzyloxy, methoxymethoxy, and tert-butyldimethylsiloxy groups, reactions favor the anti-isomer with selectivities up to anti:syn = >99:1. With a hydroxyl group, selectivities are reversed and the syn-isomer is favored with selectivities up to anti:syn = <1:99.
Belelie
Jennifer L
JL
Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1.
Chong
J Michael
JM