The asymmetric Claisen rearrangement of cis-allylic α-(trimethylsilyl)vinyl ethers with chiral organoaluminum reagent (R)-1 (methylaluminum (R)-(+)-3,3′-bis(triphenylsilyl-1, 1′-binaphthalene-2,2′-diolate) produces optically active acylsilanes [3-substituted 1-trimethylsilyl)- 4-penten-1-ones) with the same absolute configuration as those from trans-allylic α-(trimethylsilyl)vinyl ethers.