Oxirane reactions with organometallic compounds

Reactions of Oxirans with Organometallic Compounds. - A general method for the preparation of halohydrin esters via the reaction of organic halides with CO (20 atm) in the presence of PhPd(PPh3)2l has been described.In the particular case of benzyl chloride and cyclohexene oxide, (228) (57.5%) was obtained. A possible mechanism for this reaction is shown in Scheme 14. 

Nucleophilic ring-opening of oxiranes by lithium dialkylcuprates occurs at the sterically less-hindered side and the corresponding alcohol is formed.The reaction can be carried out under mOd conditions and the side-reactions observed with other organometallic compounds can be avoided. The mechanism of the transformations has been treated in detail. With MejCuLi the reaction proceeds stereoselectively and the new C-C bond is formed on the side opposite the C-0 bond of the oxirane (Eq. 

This review article is concerned with chemical behavior of organo-lithium, -aluminum and -zinc compounds in initiation reactions of diolefins, polar vinyls and oxirane compounds. Discussions are given with respect to the following five topics 1) lithium alkylamide as initiator for polymerizations of isoprene and 1,4-divinylbenzene 2) initiation of N-carboxy-a-aminoacid anhydride(NCA) by a primary amino group 3) activated aluminum alkyl and zinc alkyl 4) initiation of stereospecific polymerization of methyloxirane and 5) comparison of stereospecific polymerization of methyloxirane with Ziegler-Natta polymerization. A comprehensive interpretation is proposed for chemistry of reactivity and/or stereospecificity of organometallic compounds in ionic polymerizations. 

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