Applications of remote stereocontrol using allylstannanes: an approach to the stereoselective synthesis of aliphatic polyols

(4R,2E)-4-Benzyloxy-octa-2,7-dienyl(tributyl)stannane was transmetalated by tin(IV) chloride to generate an allyltin trichloride, which reacted with aldehydes to give (3Z)-1,5-syn-5-benzyloxynona-3,8-dien-1-ols with useful 1,5-stereocontrol. O-Benzylation, hydroboration and oxidation of the terminal double-bond of the product from 2-methylpropanal gave (5R,9S,6Z)-5,9-dibenzyloxy-10-methylundec-6-enal. Further reactions with 4-alkoxyalk-2-enylstannanes proceeded with useful 1,5-stereocontrol to give open-chain products with hydroxy or benzyloxy substituents stereoselectively disposed at remote positions along the chain.