Carbon Carbon Bond Formation

Volume 3 covers carbon-to-carbon single bond forming reactions involving sp3, sp2 and sp carbon centers, but only those which do not involve additions to C-X &pgr;-bonds. The volume first compares and contrasts the alkylation reactions of all types of sp3 carbon nucleophiles and also covers vinyl and alkynyl carbanions. Following on from Volume 2, a separate section covers Friedel-Crafts alkylation reactions, which is complemented by discussions of polyene cyclizations and electrophilic transannular cyclizations in synthesis. Coupling reactions leading to &agr;-bond formation, and involving all types of combinations ofsp3, sp2 and sp carbon centers are next covered, including those reactions based on pinacol, acyloin and phenol oxidative coupling reactions, and also the Kolbe reaction. Rearrangement reactions, leading to carbon-to-carbon &agr;-bond formation, are often used in a clever manner in synthesis. The volume includes all those rearrangement reactions based on intermediate carbonium ions and carbanions, and also includes the benzil-benzilic acid and the Wolff rearrangements. The volume closes with coverage of carbonylation reactions, and the use of carbene insertion reactions into the C-H bond in synthesis.

Textbook on modern methods of organic synthesis.

More and more possible applications of organometallic compounds in organic synthesis have been uncovered and a growing number of scientists are attracted to this area of research. This book presents an state-of-the-art account of the successful application of main- and transition metal mediated syntheses. It will stimulate new ideas and initiate further research in all areas of this fascinating chemistry.

TheprototypicalcatalyticreductiveC-Cbondformations,theFischer-Tropsch reaction [1] and alkene hydroformylation [2], were discovered in 1922 and 1938, respectively [3,4]. These processes, which involve reductive coupling to carbon monoxide, have long been applied to the industrial manufacture of commodity chemicals [5]. Notably, alkene hydroformylation, also known as the oxo-synthesis, has emerged as the largest volume application of homo- neous metal catalysis, accounting for the production of over 7 million metric tons of aldehyde annually. Despite the impact of these prototypical reductive C-C bond formations, this ?eld of research lay fallow for several decades. Eventually, the increased availability of mild terminal reductants, in part- ular silanes, led to a renaissance in the area of catalytic reductive C-C bond formation.Forexample,the'rstcatalyticreductiveC-Ccouplingsbeyond- droformylation, which involve the hydrosilylative dimerization of conjugated dienes [6-12], appeared in 1969 - approximately 16 years after the ?rst - ported metal-catalyzed alkene hydrosilylation [13]. Following these seminal studies, the ?eld of catalytic reductive C-C bond formation underwent exp- sivegrowth,culminatingintheemergenceofanevergrowingbodyofresearch encompassing a powerful set of transformations. To our knowledge, no thematic volumes devoted solely to metal-catalyzed reductive C-C bond formationhave been assembled. For the ?rst time, in this issue of Topics in Current Chemistry,wepresent acompilation ofmonographs from several leaders in this burgeoning area of research. This collection of reviews serves to capture the diversity of catalytic reductive C-C couplings presently available and, in turn, the remarkable range of reactivity embodied by such transformations. There is no indication that this ?eld has reached its zenithanditisthehopeofthepresentauthorthatthisvolumewillfuelfurther progress.