Asymmetric induction can be achieved in the ?-selective substitution reaction of allylic substrates (R'CH--CH-CH2Y) with n-BuMgl catalyzed by the chiral arenethiolatocopper(I) complex lb. It was found that the enantiomeric excess of the ?-substituted product (R'CH(n-Bu)CH--CH2) is influenced by the coordinating ability of the leaving group Y, and e.e.'s of up to 42% (1( = Cy, Y = OAc) have been obtained.The copper(I)-catalyzed cross-coupling reaction of organometallic reagents with allylic substrates is an

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AbstractÐThe in¯uence of some experimental parameters on the regio-and enantioselectivity in the g-selective substitution reaction of Grignard reagents RMgX with acyclic allylic acetates catalyzed by the arenethiolatocopper(I) complex (S)-1 was studied. When more bulky arenethiolatocopper(I) complexes than (S)-1 were employed in a reaction of allylic acetate 3 with n-BuMgI, the enantioselectivities observed for the g-product were lower. With an arenethiolatocopper(I) catalyst prepared in situ, several Grignard reagents were studied in a substitution reaction with acetate 2. Compared to n-BuMgI, more bulky Grignard reagents gave no improvement of the enantioselectivity in the formation of the g-product. q

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