The metathesis reactions: from a historical perspective to recent developments

Metathesis is one of the most spectacular recent improvements in synthetic strategies for organic synthesis and polymer science. The historical aspects and modern developments of the metathesis reactions are summarized here. In particular, emphasis is placed on the leading role played by the mechanistic work and proposals of Yves Chauvin and on the history of the efficient catalysts discovered by the groups of R. R. Schrock and R. H. Grubbs. It is pointed out how the Chauvin metathesis mechanism, with formation of a metallacyclobutane, has been generalized to many organometallic reactions that also involve square intermediates comprising a metal atom. Subsequently, the progressive development of ideas by Schrock and Grubbs during the last three decades has brought the field to the forefront of synthetic chemistry. The quest for efficient metathesis catalysts is a success story, starting from organometallic mechanisms, that has now invaded the worlds of organic synthesis and polymer science. Indeed, the Schrock’ and Grubbs’ catalysts and their derivatives are now the most efficient catalysts compatible with functional groups for the metathesis reactions. They considerably shorten synthetic schemes by affording new routes and therefore have changed the way chemists think about synthesis.