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This chapter covers the literature published during 2012 relating to the above area, apart from a few papers from 2011 in less accessible journals which came to light in Chemical Abstracts in 2012. The number of papers published in 2012 is similar to that in 2011 and again it has been necessary to continue to be selective in the choice of publications cited. Nevertheless, it is hoped that most significant developments have been noted. The year under review has again seen the publication of a considerable number of review articles and many of these are cited in the various sections of this report. Although the use of a wide range of tervalent phosphorus ligands in catalysis continues to be a major driver in the chemistry of traditional P–C-bonded phosphines (and also that of tervalent phosphorus acid derivatives, usually covered in detail elsewhere in this volume), a noteworthy feature of the literature reviewed here is a significant increase in the number of papers reporting studies of the reactivity of phosphines, in particular those involving nucleophilic attack at a carbon atom of an electrophilic substrate. Recent general reviews of phosphine ligand chemistry relevant to the catalysis area have provided coverage of recent developments in the asymmetric synthesis of chiral phosphines, (and other classes of organophosphorus compound), the synthesis of planar chiral phosphines derived from [2,2]paracyclophane, routes to P-stereogenic oligomers, polymers and related cyclic phosphines, and the stoichiometric and catalytic synthesis of alkynylphosphines. Butler has published a ‘practioner’s perspective’ on simple routes to ferrocenyl phosphine ligands.

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