This review is a comprehensive account of transitionmetal-catalyzed cross-coupling reactions to form C-P bonds. Organized according to the hybridization of the carbon coupling partner, the numerous phosphorus coupling partners are discussed individually. The several putative mechanisms of these transition-metal catalyses are also included, thereby providing insights into both the synthetic and the mechanistic aspects of this chemistry. A separate section is devoted to asymmetric C-P cross-couplings. 2.7.

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A general protocol for the conjugate transfer of diphenyl-, dicyclohexyl-, and di-tert-butylphosphinyl groups from silylphosphines to cyclic and acyclic electron-deficient acceptors employing a bench-stable palladium(II) catalyst is reported. Several E and Z configured alpha,beta-unsaturated carbonyl and carboxyl acceptors (including imides) as well as nitroalkenes participate in this palladium(II)-catalyzed process in high chemical yields.

Nucleophile-activation of the phosphorus(iii)-silicon linkage in silylphosphines generates a nucleophilic phosphorus(iii) equivalent thereby allowing for a rhodium-catalysed conjugate phosphination of beta-substituted alpha,beta-unsaturated acceptors.

Review: ca. 200 refs.