PREPARATION AND SOME REACTIONS OF ALLYLIC INDIUM REAGENTS

A variety of allylic indium sesquihalides were readily prepared by the reaction of indium powder with allylic halides in DMF at room temperature. Protonation of the allylindium reagents proceeded regiospecifically at the gamma-position of the allylic group to give 1-propenes. A facile transformation of alpha-pinene to beta-pinene was achieved via a myrtenylindium intermediate. Oxygenation of the allylic indium reagents gave mixtures of allylic alcohol isomers in moderate yields. The coupling of the allylindium reagents with cyclic imides gave diverse products depending on the structures of the substrates and the reagents. Stannylation with tributylchlorostanane occurred exclusively at the alpha-carbon, yielding allytributylstannanes; E, Z isomerization of the allylic double bond depended largely upon the substitution pattern on the allylic moiety.