Solvomercuration-Demercuration. 10. Oxymercuration-Demercuration of Olefins with the Mercuric Salts Acetate, Trifluoroacetate, Nitrate, and Methanesulfonate

Article abstract of DOI:10.1021/jo00332a009

The oxymercuration-demercuration of a series of representative olefins has been examined with four mercuric salts: acetate, trifluoroacetate, nitrate, and methanesulfonate.Mono- and 1,2-disubstituted olefins undergo hydration with all four mercuric salts in 90-100percent yields with a regioselectivity for the Markovnikov alcohol (from monoolefins) of >99.5percent.Only styrene was found to be an exception.In marked contrast, only mercuric acetate is effective for the Markovnikov hydration of 1,1-di-, tri- ,and tetrasubstituted olefins.The other three mercuric salts provide loweryields of the tertiary alcohols, yields which decrease rapidly with time. 1-Phenylcyclopentene undergoes only allylic oxidation with the mercuric salts trifluoroacetate, nitrate, and methanesulfonate.Mercuric acetate does give the normal hydration product but only in trace amounts.In this case, allylic oxidation is the major reaction pathway with this salt as well.