Handbook of Organopalladium Chemistry for Organic Synthesis

Abstract

The authors present the early concepts concerning the mechanism of the Heck reaction and its reasonable working hypotheses, followed by a discussion and summary. Carbopalladation, a central reaction in organopalladium chemistry, is extensively presented in this section including the carbopalladation reactions of allenes and the carbopalladation methodology and its employment in the synthesis of natural products. The authors discuss the successful employment of the Heck reactions in various inter-inter, intra-inter-, as well as all-intramolecular reaction cascades, and describe the termination of these processes by alkenes, arenes, and related π-bond systems such as alkynes and allenes. The authors present and discuss allylpalladation of alkenes, alkynes, and dienes as a powerful tool for preparing carbocycles and heterocycles. Pd-catalyzed homocoupling of terminal alkynes, cross-coupling of terminal alkynes with internal alkynes, and cross-coupling of terminal alkynes with allenes is presented. The formal arene analogs of the Heck reaction are discussed and examples presented. Cyclopropanation and other reactions of Pd-carbene complexes are given. Carbopalladation via palladacyclopropanes and palladacyclopropenes is outlined. The reaction of an alkyl iodide with diethylzinc in the presence of a palladium (0) catalyst is given. The combination of a radical cyclization with the formation of an organometallic product is discussed. Closely related Ni-catalyzed cyclizations are briefly presented.