Chemistry, like all the natural sciences, Category: chiral-phosphine-ligands, begins with the direct observation of nature¡ª in this case, of matter.6224-63-1, Name is Tri-m-tolylphosphine, SMILES is CC1=CC(P(C2=CC=CC(C)=C2)C3=CC=CC(C)=C3)=CC=C1, belongs to chiral-phosphine-ligands compound. In a document, author is Kirchhof, Manuel, introduce the new discover.
Experimental and Theoretical Study on the Role of Monomeric vs Dimeric Rhodium Oxazolidinone Norbornadiene Complexes in Catalytic Asymmetric 1,2-and 1,4-Additions
The influence of nuclearity and charge of chiral Rh diene complexes on the activity and enantioselectivity in catalytic asymmetric 1,2-additions of organoboron reagents to N-tosylimines and 1,4-additions to enones was investigated. For this purpose, cationic dimeric Rh(I) complex [(Rh(1))(2)Cl]SbF6 and cationic monomeric Rh(I) complex [RhOH2(2)]SbF6 were synthesized from oxazolidinone-substituted 3-phenylnorbornadiene ligands 1 and 2, which differ in the substitution pattern at oxazolidinone C-5′ (CMe2 vs CH2) and compared with the corresponding neutral dimeric and monomeric Rh(I) complexes [RhCl(1)](2) and [RhCl(2)]. Structural, electronic, and mechanistic insights were gained by X-ray crystallography, cyclic voltammetry (CV), X-ray absorption spectroscopy (XAS), and DFT calculations. CV revealed an increased stability of cationic vs neutral Rh complexes toward oxidation. Comparison of solid-state and solution XAS (extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES)) data showed that the monomeric Rh complex [RhCl(2)] maintained its electronic state and coordination sphere in solution, whereas the dimeric Rh complex [RhCl(1)](2) exchanges bridging chloro ligands by dioxane molecules in solution. In both 1,2- and 1,4-addition reactions, monomeric Rh complexes [RhCl(2)] and [RhOH2(2)]SbF6 gave better yields as compared to dimeric complexes [RhCl(1)](2) and [(Rh(1))(2)Cl]SbF6. Regarding enantioselectivities, dimeric Rh species [RhCl(1)](2) and [(Rh(1))(2)Cl]SbF6 performed better than monomeric Rh species in the 1,2-addition, while the opposite was true for the 1,4-addition. Neutral Rh complexes performed better than cationic complexes. Microemulsions improved the yields of 1,2-additions due to a most probable enrichment of Rh complexes in the amphiphilic film and provided a strong influence of the complex nuclearity and charge on the stereocontrol. A strong nonlinear-like effect (NLLE) was observed in 1,2-additions, when diastereomeric mixtures of ligands 1 and epi-1 were employed. The pronounced substrate dependency of the 1,4-addition could be rationalized by DFT calculations.
Note that a catalyst decreases the activation energy for both the forward and the reverse reactions and hence accelerates both the forward and the reverse reactions. you can also check out more blogs about 6224-63-1. Category: chiral-phosphine-ligands.
Reference:
Phosphine ligand,
,Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate