Remote stereocontrol using allylstannanes: reversal in stereoselectivity using indium(III) and bismuth(III) halides as promoters

Allyl-indium(III) and -bismuth(III) dihalides, generated by transmetallation of 5-benzyloxy-4-methylpent-2-enyl(tributyl)stannane 1, react with aldehydes with useful levels of 1,5-stereocontrol, a 93 :7 ratio of 1,5-epimers in favour of the 1,5-anti-(E)stereoisomers 7 and 11 typically being obtained using bismuth(III) iodide. The 4-benzyloxypent-2-enylstannane 4 similarly gives the 1,5-syn-(E)-hex-3-enols 13 also with ca. 93 :7, stereoselectivity.