Catalytic Desymmetrization of 1,4-Cyclohexadienyltriisopropoxysilane

Significance

The authors report the first catalytic desymmetrization of an allylsilane species using a chiral Cu(I) complex. Previously, the authors employed a stoichiometric chiral Ti(IV) complex to effect the desymmetrization of various 1,4-cyclohexadienes (Angew. Chem. Int. Ed. 2004, 43, 313). The current catalytic system accommodates a broad range of aromatic aldehydes including furyl and thienyl substituents. The mechanism is suggested to involve initial transmetallation of 1 to give the reactive allyl metal species 3 which via a six-membered chair transition state (6) and subsequent hydrolysis gives syn- 2.