Formation of carbon-phosphorus bonds

The use of an electron-rich trivalent phosphorus center for addition to or substitution at an electrophilic site is a long-established approach to the formation of carbon-phosphorus bonds. The classical studies of the Michaelis-Arbuzov, Michaelis-Becker, Abramov, Pudovik, and related reactions and their mechanisms and synthetic utilities have been thoroughly reviewed. In this chapter, we present only a brief introduction to these reactions and provide several examples of their more facile uses from the older literature. More attention is given to relatively recent developments regarding such reactions that are seen as improvements in their general utility. 

We begin, however, with a brief consideration of a group of phosphorus compounds of significance for their utility in the formation of carbon-phosphorus bonds via reaction with organometallic reagents in displacement reactions. 

It was recognized very early that Grignard reagents could be used for displacement of halogen on phosphorus with the attendant formation of carbon-phosphorus bonds. The formation of tertiary... 

The fourth edition has been expanded by a chapter on the Formation of Carbon-Phosphorus Bonds and by another on the Formation of Carbon-Deuterium Bonds . The chapter on Alteration of Nitrogen Groups in Carbon-Nitrogen Compounds has been substantially expanded, but the remaining parts of the book have merely been completed by inclusion of preparative processes discovered in recent years. 

One of the most versatile methods for the formation of carbon-phosphorus bonds involves the reaction of an ester of trivalent phosphorus with an alkyl halide. 

Arbuzov and Michaelis-Becker reactions provide facile and versatile procedures for the formation of carbon-phosphorus bonds. These methods, however, are not applicable to the formation of sp hybridized carbon-phosphorus bonds. Only few methods have been reported for the syntheses of arylphosphonates and vinylphospho-nates. Direct reaction of aryl or vinyl halides with trialkyl phosphite in the presence of nickel halide requires severe reaction conditions [21,22], and the stereochemistry of vinylphosphonates has not been clarified. Synthesis of dialkyl arylphosphonates 22 [23, 24] is achieved by the palladium-catalyzed reaction (Scheme 2.12), which is called by Hirao reaction . The stereoselective synthesis of dialkyl vinylphosphonates 23 [24-26] is similarly accomplished by this method (Scheme 2.13). A variety of modified procedures have been developed recently [27-37]. 

Xu Y Zhang J. Stereochemistry at the phosphorus atom during palladium-catalyzed formation of carbon-phosphorus bonds and mechanistic implications. J. Chem. Soc., Chem. Commun. 1986 1606. 

The use of palladium catalysis in the formation of carbon-phosphorus bonds has been demonstrated in the reaction of aryl iodides with secondary phosphine oxides. The reaction is successful with diaryl, dialkyl, and alkylaryl phosphine oxides as well as with... 

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