NDLI: Theoretical Studies of Asymmetric Hydroformylation Using the Rh(R,S)-BINAPHOS Catalyst—Origin of Coordination Preferences and $Stereoinduction^{†}$

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Theoretical Studies of Asymmetric Hydroformylation Using the Rh(R,S)-BINAPHOS Catalyst—Origin of Coordination Preferences and $Stereoinduction^{†}$

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Theoretical Studies of Asymmetric Hydroformylation Using the Rh(R,S)-BINAPHOS Catalyst—Origin of Coordination Preferences and $Stereoinduction^{†}$

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Carbó, Jorge J. Aguado-ullate, Sonia Guasch, Laura Saureu, Sergi
Description	Author Affiliation: Aguado-Ullate S ( Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Campus Sescelades, Marcel.lí Domingo s/n, 43007 Tarragona, Spain.)
Abstract	We have undertaken theoretical investigations of the asymmetric hydroformylation of styrene by the $[Rh\{(R,S)-BINAPHOS\}(CO)_{2}H]$ catalyst, focusing on the origin of the ligand coordination preferences and stereoinduction. We evaluated the different factors governing the preference of the BINAPHOS ligand to coordinate with the phosphane moiety at the equatorial site and the phosphite moiety at the apical site. The donor–acceptor interactions, obtained using a modified version of energy decomposition analysis (EDA) based on orbital deletion, favour the phosphite moiety at the equatorial site. However, the electronic distortion and the steric effects inverse this tendency. Calculations also suggest that the coordination preference was transferred to the selectivity-determining transition state. We propose a stereochemical model based on quantitative quadrant maps obtained from a new molecular descriptor, the distance-weighted volume $(V_{W}),$ which is easily computed from ground-state structures. Repulsive interactions between the substrate and the apical phosphite were responsible for the enantiodifferentiation. The axial chirality of the phosphite discriminated one of the competitive equatorial–apical paths, whereas the axial chirality of the backbone discriminated one of the two enantiomers. Transition-state calculations revealed that the placement of phosphane at the apical site would lower enantioselectivity, explaining the poor performance of other phosphane–phosphite ligands. Finally, comparison with previous studies allowed the definition of several prerequisites for diphosphane ligands for high stereoselectivity: 1) specific equatorial–apical coordination bringing chirality to the apical site, 2) combination of two stereogenic centres and 3) rigid structures.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	3
Volume Number	18
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2012-01-16
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Models, Theoretical Organophosphorus Compounds Chemistry Catalysis Models, Molecular Molecular Conformation Molecular Structure Stereoisomerism Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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