Tandem silylformylation–allyl(crotyl)silylation: a new approach to polyketide synthesis

Abstract Tandem intramolecular silylformylation–allyl(crotyl)silylation reactions have been developed that allow the highly efficient synthesis of polyketide fragments. The substrates are subjected to Rh(I)-catalyzed silylformylation to afford β-(diallyl)silyl aldehydes which undergo spontaneous uncatalyzed allylsilylation. This unusual spontaneous allylsilylation reaction is driven by strain release Lewis acidity, which arises from the ∼95° O–Si–C bond angle in the oxasilacyclopentane product of the silylformylation reaction. The methodology has been developed both for alkene and alkyne substrates, may be used to establish as many as three stereocenters, and has been shown to be amenable to use in an iterative fashion.