Homoallylic and bishomoallylic alcohols

Allylic and cis-homoallylic alcohols are epoxidized readily, but frans-homoallylic and bishomoallylic alcohols react slowly, if at all. The stereoselectivity in the epoxidation of acyclic allylic alcohols is the same as and is comparable to that observed with r-BuOOH/VO(acac)2. The stereoselectivity in epoxidation of acyclic homoallylic alcohols is also the same but lower than that obtained with t-BuOOH/ VO(acac)2. Epoxidation of cyclic allylic alcohols proceeds more slowly and in lower yield than that of acyclic allylic alcohols. 

The related (Z)-lithium dialkenylcuprates (147) derived from acetylene itself also react well with epoxides to provide a useful route to (2)-homoallylic alcohols the lack of reactivity with esters allows an easy access to lactones (148) by condensations between epoxy esters and this type of cuprate (Scheme 29). Likewise, the lower homologs (149) and (151), both of which are relatively easy to prepare in optically active forms, can be readily converted into homoallylic and bishomoallylic alcohols (150) and (152) respectively. An ester unit can also be incorporated into the cuprate functions thus, addition of a mixed lithium cuprate, RCuYLi , to ethyl propiolate gives the cuprates (153), which add to epoxides to give unexpectedly the (Z)-crotonates (154). Such isomerization is not uncommon with vinyl carbanions in general, and is obviously a limitation when isomeric mixtures are produced. 

Li Z, Yamamoto H. Zirconium(IV)- and hafnium(IV)-cata-lyzed highly enantioselective epoxidation of homoallylic and bishomoallylic alcohols. J. Am. Chem. Soc. 2010 132 (23) 7878-7880. 

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