An Overview of the Synthesis of Alkenylphosphines

Alkenylphosphines are compounds of great interest in view of their structures. Hence, these phosphorus derivatives bear a carbon- carbon double bond, directly linked to the phosphorus atom. This insaturation may be used as a coordinating part in presence of a metal or as a reactive part in contact with an electrophile. Thus, alkenylphosphines have found numerous applications in various fields of chemistry. They are useful intermediates in organic synthesis, as precursors of polyphosphines or dendrimers, or as dienophiles in cycloaddition reactions. Due to the presence of both the phosphorus atom and the carbon-carbon double bond, they are of great interest in coordination chemistry. Recently, they were also used as ligand in homogeneous catalysis. Alkenylphosphines are mainly prepared by reaction between halophosphines and alkenyl organometallic species, by hydrophosphination of alkynes or by C-P cross-coupling reactions. The aim of this review will be to describe these methods, emphasizing particularly on the catalytic ones. The new methodologies involving the functionalization of alkynylphosphines and the bis-functionalization of alkynes, which recently appeared in the literature will also be documented. Less commonly used reactions such as alkylation of primary or secondary vinylphosphines, reduction of phosphine-oxides or phosphinates will be briefly reported.