Design of Ionic Phosphites for Catalytic Hydrocyanation Reaction of 3‐Pentenenitrile in Ionic Liquids^†

Abstract

Abstract:The synthesis and characterization of a novel class of ionic phosphites bearing either a single cationic group obtained by quaternization of aminophosphites or three cationic groups prepared by reaction of phosphorus trichloride with imidazolium phenols are reported. The catalytic hydrocyanation reaction of 3-pentenenitrile (3PN) into adiponitrile has been performed in the presence of Ni(0) with ionic phosphite ligands, and a Lewis acid in biphasic ionic liquid/organic solvent system. The screening of several original cationic phosphites was performed and the experimental conditions were optimized for the tricationic phosphite tris-4-[(2,3-dimethylimidazol-1-yl) methyl]phenyl phosphite tris[bis(trifluoromethylsulfonyl)amide]. It is possible to obtain performance similar to molecular systems and the catalyst and the Lewis acid were immobilized in the ionic phase.

Chiral Ionic Phosphites and Diamidophosphites: A Novel Group of Efficient Ligands for Asymmetric Catalysis

“…Unlike the traditional synthetic approach to ionic phosphites through quaternization of P,N-bidentate compounds, [6] the novel phosphites and diamidophosphites L1-L3 were synthesized by a direct phosphorylation of an appropriate ionic liquid in CH 2 Cl 2 (Scheme 1).…”

“…[14] Table 3 and Table 4 show that activity (and enantioselectivity) depend upon the nature of the ligand, a conclusion noted earlier in other systems. [6] …”

“…[8,14] Preparation of 1-(2-Hydroxyethyl)-3-heptylimidazolium Tetrafluoroborate A mixture of 1-(2-hydroxyethyl)-3-hepthylimidazolium chloride (obtained similar to the literature [6] without characterization) (8.0 g, 0.032 mol), KBF 4 (12.6 g, 0.1 mol) and dry acetonitrile (50 mL) was heated to reflux with stirring for 48 h. Upon cooling, the white precipitate was filtered off and washed with acetonitrile (3 20 mL). The organic fil- …”

“…However, recently a study regarding the use of ionic forms of achiral phosphites in catalysis appeared. [6] Moreover, a chiral ionic phosphoramidite was described, but it was not used directly in catalysis. [7] Herein we report the synthesis of chiral cationic phosphites and diamidophosphites along with their application in the Rh-catalyzed asymmetric hydrogenation of prochiral olefins and Pd-catalyzed allylation as well as their successful immobilization by ionic interaction on an anionic support.…”

Helicene‐Based Phosphite Ligands in Asymmetric Transition‐Metal Catalysis: Exploring Rh‐Catalyzed Hydroformylation and Ir‐Catalyzed Allylic Amination

“…After optimizing the reaction conditions, we found that sodium alcoholate generated from optically pure (+)-(P,S)-18 reacted smoothly with commercially available chlorophosphites 19 and 20 or chlorophosphites 21 [30] and 22, [31] whose syntheses have been described in the literature. The formation of phosphites could be easily monitored by 31 P{ 1 H} NMR spectroscopy, as the conversion of chlorophosphites into phosphites was indicated by a significant shift in the signal of the phosphorus atom (for the chemical shifts of phosphorus atoms in chlorophosphites 19-22 and phosphites 23-26, see the Supporting Information).…”