Intramolecular coupling of allyl carboxylates with allyl stannanes and allyl silanes: a new type of reductive elimination reaction?

Abstract

The palladium-catalyzed intramolecular coupling of allyl stannanes with allyl carboxylates provides a general synthesis of five- and six-membered-ring carbocycles. The intramolecular coupling leads selectively to trans five-membered carbocycles and cis six-membered carbocycles, regardless of the cis or trans configuration of the allylic functions in the starting material. For example, the stereoselective synthesis of 10-epi-elemol demonstrated the cis configuration of the six-membered carbocycles. The related Oppolzer cyclization leads to lower yields, or fails completely, with substrates substituted at C-3 of the allyl and/or alkene terminus. The palladium-catalyzed intramolecular coupling of allyl silanes with allyl trifluoroacetates allows the synthesis of trans five-membered-ring carbocycles and requires the use of a bicyclic phosphite as the ligand. DFT calculations suggest that the preferred pathway for the intramolecular allyl/allyl coupling is by formation of the Cbond;C bond between the C-3 termini of the allyl ligands of bis(eta(3)-allyl)palladium complexes.