Electronic Differences between Coordinating Functionalities of Chiral Phosphine−Phosphites and Effects in Catalytic Enantioselective Hydrogenation

Citations Over TimeTop 10% of 2002 papers

Abstract

A convenient synthesis of new chiral phosphine−phosphites (P−OP) has been described. The versatility of the synthetic protocol developed has allowed the preparation of ligands with different phosphine fragments and the choice of the stereogenic element location. Analyses of the values of 1JPSe of the corresponding diselenides are in accord with the expected lower σ-donor ability of the phosphite fragment, with respect to the phosphine group, and with an increase of phosphine basicity after substitution of phenyl substituents by methyl groups. Inspection of υ(CO) values on a series of complexes RhCl(CO)(P−OP) demonstrated a variable π-aceptor ability of the phosphite group, compensating for the change of basicity of the phosphine functionality, as well as having a rather reduced electron density at the metal center compared with diphosphine analogues. The distinct nature of the phosphorus functionalities has also been evidenced in rhodium-catalyzed enantioselective hydrogenation of methyl Z-α-acetamido-cinnamate (MAC). Thus, the coordination mode of the substrate is governed by the chiral ligand, directing the olefinic bond to a cis position with respect to the phosphite group, as demonstrated by NMR studies performed with [Rh(P−OP)(MAC)]+ complexes. In consequence, the phosphite group has a greater impact on the enantioselectivity of the product. However, the optical purity of the process also depends on the nature of the phosphine group, and hence, an appropriate election of both phosphorus functionalities is required for the attainment of excellent enantioselectivities (99% ee).

Related Papers

• → Recent Advances in the Transition‐Metal‐Catalyzed Enantioselective Synthesis of Silicon‐Stereogenic Organosilanes(2015)126 cited
• → Enantioselective Organocatalyzed Formal [4+2] Cycloaddition of Ketimines with Allenoates: Easy Access to a Tetrahydropyridine Framework with a Chiral Tetrasubstituted Stereogenic Carbon Center(2014)59 cited
• → Enantioselective Formation of Cyano‐Bearing All‐Carbon Quaternary Stereocenters: Desymmetrization by Copper‐Catalyzed N‐Arylation(2014)13 cited
• → Organocatalytic Enantioselective Synthesis of P‐Stereogenic Chiral Oxazaphospholidines(2016)26 cited
• → Catalytic Asymmetric Synthesis of Silicon-Stereogenic Compounds by Enantioselective Desymmetrization of Prochiral Tetraorganosilanes(2018)19 cited