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The Origins of Enantioselectivity in Rh–Diene Complex Catalysed Arylation of Cyclohex‐2‐enones
Author(s) -
Gosiewska Silvia,
Raskatov Jevgenij A.,
Shintani Ryo,
Hayashi Tamio,
Brown John M.
Publication year - 2012
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.201102421
Subject(s) - diene , chemistry , steric effects , conjugate , cyclohexenone , aryl , combinatorial chemistry , stereochemistry , catalysis , density functional theory , computational chemistry , organic chemistry , mathematics , mathematical analysis , natural rubber , alkyl
Chiral diene ligands : Conjugate addition of aryl boronic acids to cyclohexenone is catalysed by Rh complexes of the simple chiral diene ( S )‐bicyclo[3.3.1]nona‐2,6‐diene in unexpectedly high ee. Insight into the reasons, and more generally the TS structure and pathways with other catalysts, was explored by using density functional theory. There was a gratifyingly good agreement between calculation and experiment. A lack of obvious steric discrimination together with systematic variations in TS structure implicated stereoelectronics.