“…Here, using the isolated ortho -cyclometalated π-allyl iridium precatalyst derived from [Ir(cod)Cl] 2 , 4-cyano-3-nitrobenzoic acid, ( R )-SEGPHOS, and allyl acetate, we report that α-(trimethylsilyl)allyl acetate 1a couples to carbonyl compounds from the aldehyde or alcohol oxidation level, respectively, with exceptional levels of regio- and anti -diastereo- and enantioselectivity (Scheme ). In this fashion, α-(trimethylsilyl)allyl acetate serves as an alternative to previously reported silicon-containing 1,3- or 1,1-bimetallic allyl transfer agents. − As demonstrated in the case of adduct 4g , the products of (trimethylsilyl)allylation are readily converted to 1,4-ene-diols upon DMDO oxidation. , Additionally, conditions for proto-desilylation with allylic transposition have been identified in the absence of a hydroxyl protecting group. Finally, upon exposure to chlorosulfonyl isocyanate, formal [3 + 2] cycloaddition occurs to deliver γ-lactams possessing three contiguous stereogenic centers as single diastereomers.…”