Phosphorus nucleophiles transition-metal catalysts

The breaking of carbon-to-phosphorus bonds is by itself not a useful reaction in homogeneous catalysis. It is an undesirable side-reaction that occurs in systems containing transition metals and phosphine ligands and that leads to deactivation of the catalysts. Two reaction pathways can be distinguished, oxidative addition and nucleophilic attack at the co-ordinated phosphorus atom (Figure 2.35). 

Recently, Gladysz et al. have developed an effective chiral rhenium-containing phosphine (294) catalyzed intramolecular MBH reaction of enone-aldehydes 295 in benzene, affording the corresponding adducts 296 in 88-99% yields with 38-74% ee (Scheme 1.107). Notably, the catalyst loadings can be much lower than those required with organophosphines, presumably due to the transition-metal-enhanced phosphorus nucleophilicities. ... 

Transition metal-catalyzed C—P cross-coupling affords powaful tool for the preparation of aryl phosphorus compounds [198]. The scope of the phosphorus-based nucleophiles used in crosscoupling with aryl electrophiles in the presence of transition metal (Pd-, Cu-, and Ni-based) catalysts is very broad. Figure 20.5 summarizes the common phosphoms nucleophiles used for crosscoupling reactions (for mechanism, see Scheme 20.2). 

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