Tervalent Phosphorus Acid Derivatives

This chapter covers the published literature, during the year 2014, related to the development of tervalent phosphorus acid derivatives. The number of papers published required a critical selection of the bibliographic material, where the most relevant papers based on the synthesis of new tervalent phosphorus acid derivatives, the synthesis of organometallic compounds and also their applications in catalysis have been covered. Several reviews have been published in the field, with a particular emphasis on their catalytic applications. 

Department of Chemistry, University of Coimbra, Rua Largo, 3004-535, Coimbra, Portugal. E-mail mmpereira qui.uc.pt 

These complexes have also been used as precursors to transient alkoxy phosphinidenes which may be trapped with allgmes. Moreover, computational studies on the chloro, alkojgr, and related amino and allg l phosphinidenes showed that chloro and alkojgr phosphinidenes have minimal Ti-donation to P from Cl or -OR, in contrast to stable amino-phosphinidenes, which have significant N to P 7t-donation. 

A review on the reaction of quinones with phosphorus-containing reagents, including phosphites, phosphinites, and phosphonites, has appeared. Another review has been published on the synthesis and reactivity of tervalent fluoro-alkoxy derivatives of phosphorus.  

As this area was not covered in Volume 31, the present chapter provides an overview of the literature published over the two years between July 1998 and June 2000. The report is structured in terms of the principal classes of tervalent phosphorus acid derivatives, viz halogenophosphines, tervalent phosphorus esters, and amides. Attempts have been made to minimise the extent of overlap with other chapters, in particular those concerned with the synthesis of nucleic acids and nucleotides to which the chemistry of tervalent phosphorus esters and amides contributes significantly (see Chapter 4), the use of known halogenophosphines as reagents for the synthesis of phosphines (see Chapter 1), and the reactions of dialkyl- and diaryl-phosphite esters, in which the contribution of the phosphonate tautomer, (R0)2P(0)H, is the dominant aspect. 

Organophosphorus Chemistry, Volume 32 The Royal Society of Chemistry, 2002 

A number of non-routine reactions of halogenophosphines are worthy of note. The first aliphatic phosphenium cation featuring a phosphorus-sulfur bond (17) has been obtained by treatment of the chlorophosphine (18) with aluminium trichloride in dichloromethane solution. A new synthesis of acyclic chiral t-phosphines has been developed which employs selective, sequential alkylation of the chloro(amino) phosphines (19) by Grignard and organolithium reagents. The key intermediates (19) are readily prepared by the 

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The main area of activity this year has again been the use of tervalent phosphorus acid derivatives for preparation of phosphates or modified phosphates of biochemical interest. Most of this work is reported in part 3.3 of this chapter. 

Miscellaneous. - Several new optically active tervalent phosphorus acid derivatives have been prepared for use as ligands in asymmetric metal catalysed reactions. These include the cyclic diaminophosphines 57, the cyclic bisamino-phosphine 58, and the compounds 59, 60, 61, and 62 containing a 1,1 -binaphthalene group as the chiral inducer. A new diphosphoramidite (63) has been used for improved regioselectivity of rhodium-catalysed hydroformylations of alkenes. A new sterically hindered chiral phosphite (64) derived from glucose and a Cu(I) complex of 64 have been prepared. ... 

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