The Development of Bidentate P,N Ligands for Asymmetric Catalysis

Abstract

In this review, an attempt is made to systemise the ro √ le which bidentate phosphinamine (P,N) ligands play in asymmetric catalysis. The ligands will be classified, not by the reaction to which their metal complexes have been applied, but by the nature of their donor atoms. In this manner the development of ligand architectural design can be more easily monitored. The asymmetric transformations to which metal complexes of these ligands have been applied include among others, palladium-catalysed allylic substitutions, copper-catalysed 1,4-additions to enones and rhodiumcatalysed hydroboration of vinylarenes. Excellent enantioselectivities, regioselectivities and reactivities have been achieved in each of these processes.

STRUCTURAL AND PHOTOPHYSICAL PROPERTIES OF A MONONUCLEAR Re(I) COMPLEX:[P,N-{(C6H5)2(C5H5N)P}Re(CO)3Br]

“…hardness, coordinating ability or trans-effect, add possibilities during a for example catalytic cycle, which could be used to tune the reaction to a specific target. [1][2][3][4][5][6] Particularly, many attention have been devoted to the molecule diphenylpyridylphosphine, (C 6 H 5 ) 2 (C 5 H 5 N)P, synthesized 35 7 years ago (structurally determined in 1989 8 ). The molecule is a rigid bidentate ligand with a short bite of 2.5 Å (see scheme 1).…”

Synthesis and Structure of Trinuclear W3S4Clusters Bearing Aminophosphine Ligands and Their Reactivity toward Halides and Pseudohalides

“…In the last years, aminophosphines have emerged as versatile ligands because they combine the π-acceptor character of the phosphorous atom with the σ-donor properties of nitrogen. [12][13][14] In addition, the NH moieties from the aminophosphine directly coordinated to the metal centre, can take part in the catalytic reaction by cooperation with the metal-bonded species. 1 A priori several isomeric forms are feasible upon coordination of a bifunctional ligand, such as aminophosphine, to the Mo 3 S 4 unit assuming an analogous coordination to that of diphosphines as illustrated in Figure 2.…”

Stereoselective Construction of Quaternary Stereocenters

“…[21] Stoltz and Behenna recently published the first asymmetric version of this Tsuji allylation. [22] The P,N ligand 22 [23] was used for intramolecular conversion of enol carbonate 21 to ketone 23 (Scheme 6). Both yield and stereoselectivity were good.…”