Design of catalytic processes based on studies of elementary processes

In the first part of the review, the personal reminiscences of the development period of organometallic chemistry are described referring to the unexpected discoveries of late transition metal alkyls through the effort of finding an active species involved in catalysis. The isolation and examination of the behavior of these transition metal complexes led to findings of elementary processes important in catalysis. In the second part of the account, applications of the newly found elementary processes to organic syntheses are described, with emphasis on the recent development of environmentally benign catalytic processes utilizing the concept of the C–O bond cleavage in carboxylic acid derivatives combined with other elementary processes. The recently developed catalytic processes include conversion of carboxylic anhydrides and acids into aldehydes, ketones, perfluoroketones, benzylation of olefins, and conversion of allylic formates into unsaturated carboxylic acids.