Abstract
Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, is the method of choice for preparing primary and secondary alkynylphosphines, while the former strategy is usually employed for the synthesis of tertiary alkynylphosphines or their borane complexes. The classical C–P bond forming methods rely on the reaction between halophosphines or their borane complexes with terminal acetylenes in the presence of a stoichiometric amount of organometallic bases, which precludes the access to alkynylphosphines bearing sensitive functional groups. In less than a decade, efficient catalytic procedures, mostly involving copper complexes and either an electrophilic or a nucleophilic phosphorus reagent, have emerged. By proceeding under mild conditions, these new methods have allowed a significant broadening of the substituent scope and structure complexity.
Highlights
Alkynylphosphines are relevant versatile compounds due to the presence of two important functions, a phosphorus atom—a key-atom in metal coordination [1]—and an alkynyl moiety, which can coordinate to metals and is known to display a rich and diverse chemistry [2].In the past, these phosphines were mainly used in coordination chemistry for the assembly of various mono- or bi-metallic complexes and clusters [3], by taking advantage of their diverse coordination modes to transition metals, via the phosphorus atom and/or the triple bond
It is noteworthy that the range of alkynylphosphines involved in those complexes and clusters is almost exclusively covered by diphenylphosphino-phenylacetylene and bis(diphenylphosphino)acetylene
It is only recently that the high potential of alkynylphosphines as ligands for homogeneous catalysis has emerged through a few relevant catalytic applications [4]
Summary
Alkynylphosphines are relevant versatile compounds due to the presence of two important functions, a phosphorus atom—a key-atom in metal coordination [1]—and an alkynyl moiety, which can coordinate to metals and is known to display a rich and diverse chemistry [2]. The classical method for preparing alkynylphosphines is based on the nucleophilic substitution reaction at the phosphorus atom of a halophosphine by a metal (lithium, magnesium, titanium or zinc) acetylide at low temperature (Scheme 1, path A). This methodology was recently successfully applied to the synthesis of a few enantioenriched P-stereogenic alkynylphosphine-boranes. Strategies A–F for the synthesis of alkynylphosphines and/or their borane complexes Catalytic variants of this reaction have been recently described as useful alternative approaches when sensitive functional groups are present (Scheme 1, path B). The methods based on the transformation of alkynylphosphorus derivatives will be detailed
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