Carbon-phosphorus bonds formation

Several new sections have been added to this Second Edition, and the presentations of the established methods have been updated to emphasize the recent advances in their use. In addition to the survey of the approaches toward carbon-phosphorus bond formation, details of specific preparations are provided as guides for the performance of these reactions without detailed recourse to the original literature. In this way, this work is anticipated to be of particular value to the synthetic organic chemist who is skilled in the general art but not particularly experienced in organophosphorus chemistry. 

Carbon-phosphorus bond formation involving phosphorane intermediates... 

Intramolecular alkyl transfer is a fundamental problem with this reaction this problem can be addressed with modification in structure of the reagents. Neutral trivalent phosphorus reagents do react with carbonyl compounds at much lower temperatures, but lead to several types of pentacoordinated phosphorus products.190-198 More will be noted about the use of such pentacoordinated phosphorus species for carbon-phosphorus bond formation in Chapter 5. 

Wynberg, H. and Snaardijk, A.A., Asymmetric catalysis in carbon-phosphorus bond formation, Tetrahedron Lett., 5899, 1983. 

Common "parent" phosphorus-halogen species include particularly the P(III) system PC13 and the P(V) species P(0)C13. Of course, the pentacoordinated species PC15 must also be considered for its availability as reagent precursor. These are species that often serve not only in a direct manner in carbon-phosphorus bond formation but also in the construction of partially or fully esterified species prior to carbon-phosphorus bond incorporation. 

Lithium salts of resonance-stabilized organic anions have also found a role in carbon-phosphorus bond formation by displacement at phosphorus. The generation of the lithium salt derived from acetonitrile (or other aliphatic nitriles by reaction with butyl lithium or lithium diisopropylamide) provides for carbon-phosphorus bond formation by displacement of halide from phosphorus (Equation 4.24).68... 

The lithium salt of a substituted cyclopentadienyl anion has been used in reaction with phosphorus trichloride for carbon-phosphorus bond formation.70 The resultant simple displacement product ultimately undergoes dimerization and loss of four (from the dimer) equivalents of HC1 (Equation 4.25). 

In this chapter, we consider two aspects of carbon-phosphorus bond formation as they relate to pentacoordinated phosphorus species. The first aspect is the preparation of stable phosphorane species — compounds bearing five bonds to phosphorus with at least one of them being a C-P linkage. At present, this is an area of rather specialized interest, but one that has potential for broader applications. 

Hirao, T., Masunaga, T., Yamada, N., Oshiro, Y., and Agawa, T., Palladium-catalyzed new carbon-phosphorus bond formation, Bull. Chem. Soc. Jpn., 55, 909, 1982. 

Carbon-nitrogen bond formation, by reductive amination, 59, 1 Carbon-phosphorus bond formation, 36, 2 Carbonyl compounds, addition of... 

Besides the successful development of asymmetric syntheses with carbon-carbon bond formation, methods for carbon-heteroatom bond formation were also investigated intensively. In this context we developed several practical protocols for carbon-nitrogen, carbon-oxygen, and carbon-phosphorus bond formation. 

Carbon-Nitrogen and Carbon-Phosphorus Bond Formation (Table 2)... 

Oshikawa, T.. and Yamashita, K., Preparation of fosfomycin diesters by stereoselective carbon-phosphorus bond formation, Nippon Soda, lapanese Patent Appl. JP 07324092, 1995 Chem. Abstr, 124, 232132, 1996. 

A carbon-phosphorus bond formation can be accomplished by the reaction of fluoroalkanesulfonates with 0,0-dialkyl phosphonates in the presence of Pd(0)134,135 (equation 116). The method has been used to replace the phenolic OH in tyrosine by a diethoxyphosphinyl group135. 

---