Triply Convergent, Stereospecific Alkene Formation via Peterson Olefination

Article abstract of DOI:10.1021/jo00002a028

α-Iodo silanes 8 were prepared from α-hydroxy silanes and after halogen/metal exchange and treatment with copper(I)bromide-dimethyl sulfide were coupled with acid chlorides to yield α-silyl ketones 2.Cram controlled addition with a variety of nucleophiles followed by treatment with acid or base led to either the (E)- or (Z)-alkene in good overall yields from the iodide (47-67percent) and with excellent stereoselectivities (>95/<5 for disubstituted cases and 67/33 to 95/5 for trisubstituted).The procedure was used iteratively in the total synthesis of 4(E)8(Z)-tetradecadien-1-yl acetate (15) in >95/<5 isomeric purity.