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A First‐Principles Examination of the Asymmetric Induction Model in the Binap/Rh I ‐Catalysed 1,4‐Addition of Phenylboronic Acid to Cyclic Enones by Density Functional Theory Calculations
Author(s) -
Qin HuaLi,
Chen XiaoQing,
Huang YiZhen,
Kantchev Eric Assen B.
Publication year - 2014
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201402451
Subject(s) - chemistry , asymmetric induction , density functional theory , diastereomer , binap , catalysis , computational chemistry , enantiomeric excess , implicit solvation , stereoselectivity , enantioselective synthesis , solvation , stereochemistry , organic chemistry , molecule
First‐principles modelling of the diastereomeric transition states in the enantiodiscrimination stage of the catalytic cycle can reveal intimate details about the mechanism of enantioselection. This information can be invaluable for further improvement of the catalytic protocols by rational design. Herein, we present a density functional theory (IEFPCM/PBE0/DGDZVP level of theory) modelling of the carborhodation step for the asymmetric 1,4‐arylation of cyclic α,β‐unsaturated ketones mediated by a [(binap)Rh I ] catalyst. The calculations completely support the older, qualitative, pictorial model predicting the sense of the asymmetric induction for both the chelating diphosphane (binap) and the more recent chiral diene (Phbod) ligands, while also permitting quantification of the enantiomeric excess ( ee ). The effect of dispersion interaction correction and basis sets has been also investigated. Dispersion‐corrected functionals and solvation models significantly improve the predicted ee values.