THE DIRECT FORMATION OF FUNCTIONALIZED ALKYL(ARYL)ZINC HALIDES BY OXIDATIVE ADDITION OF HIGHLY REACTIVE ZINC WITH ORGANIC HALIDES AND THEIR REACTIONS WITH ACID-CHLORIDES, ALPHA,BETA-UNSATURATED KETONES, AND ALLYLIC, ARYL, AND VINYL HALIDES

Highly reactive zinc, prepared by the lithium naphthalenide reduction of ZnCl2, readily undergoes oxidative addition to alkyl, aryl, and vinyl halides under mild conditions to generate the corresponding organozinc compounds in excellent yields. Significantly, the reaction will tolerate a spectrum of functional groups on the organic halides. Accordingly, this approach can now be used to prepare a wide variety of highly functionalized organozinc compounds. In the presence of Cu(I) salts, the organozinc compounds cross-couple with acid chlorides, conjugatively add to alpha,beta-unsaturated ketones, and regioselectively undergo S(N)2' substitution reactions with allylic halides. They also cross-couple with aryl or vinyl halides with Pd(0) catalysts.