Alkyl Metals

Abstract

The preparation of bonds between metals and sp 3 -hybridized carbons is reviewed, with an emphasis on work reported since 1994. Preparation of alkyllithium derivatives by halogen–lithium exchange, halogen–lithium interconversion, deprotonation with lithiated bases, transmetallation, and alkene carbolithiation is described, and of alkylmagnesium derivatives, including Grignard reagents, by oxidative addition of magnesium metal, transmetallation and alkene carbomagnesation. Preparation of alkyl derivatives of Groups 3–10 transition metals are outlined for the main oxidation states of each metal. Transmetallation, oxidative addition, and alkylation are the most general methods described for these derivatives. Specific methods, such as alkene hydrozirconation, are also described where appropriate. Methods for the preparation of alkylcopper derivatives are presented under the categories of homo-, mixed, and heterocuprate derivatives. Preparations of alkylzinc derivatives by oxidative addition, halogen–zinc interconversion, and alkene carbozincation are discussed. Preparation of alkylaluminum derivatives by hydroalumination, carboalumination, and other methods, and of alkyltin derivatives by transmetallation, oxidative addition, and hydrostannation, are described. In addition to those metals specifically mentioned or covered above, preparation of alkylsodium, -potassium, -rubidium, -caesium, -berylium, -calcium, -strontium, -barium, -silver, -gold, -cadmium, -mercury, -gallium, -indium, -thallium, and -lead derivatives is also discussed.