Transition carbon-phosphorus bond formation

It has been known for many years that transition metals catalyze reactions of coordinated phosphines (2). Known reactions of phosphines as ligands include carbon-hydrogen lx)nd cleavage (cyclometalation), as well as direct carbon-phosphorus bond cleavage. Such metal-catalyzed reactions of phosphines lead to formation of new metal complexes which can affect catalyst properties. A known example is the reaction of triphenylphosphine to propyldiphenylphosphine during the rhodium-catalyzed propylene hydrogenation or hydroformylation (5). 

This compilation embraces a wide variety of subjects, such as solid-phase and microwave stereoselective synthesis asymmetric phase-transfer asymmetric catalysis and application of chiral auxiliaries and microreactor technology stereoselective reduction and oxidation methods stereoselective additions cyclizations metatheses and different types of rearrangements asymmetric transition-metal-catalyzed, organocatalyzed, and biocatalytic reactions methods for the formation of carbon-heteroatom and heteroatom-heteroatom bonds like asymmetric hydroamina-tion and reductive amination, carboamination and alkylative cyclization, cycloadditions with carbon-heteroatom bond formation, and stereoselective halogenations and methods for the formation of carbon-sulfur and carbon-phosphorus bonds, asymmetric sulfoxidation, and so on. 

These reagents are usually prepared by treatment of a phosphine with an alkyl halide and successive addition of base, like BuLi or NaHMDS. Reaction with the ketone takes place by attack of the carbanionoid carbon of the ylide form on the electrophilic carbon of the carbonyl group via a four-membered heterocyclic transition state, the oxaphosphetane 35. The driving force for this transformation is provided by formation of the very strong phosphorus-oxygen bond. Subsequent collapse of the oxaphosphetane furnishes the desired exomethylene group under retention of geometry. 

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