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DFT/MM Study on Copper‐Catalyzed Cyclopropanation – Enantioselectivity with No Enthalpy Barrier
Author(s) -
DrudisSolé Galí,
Maseras Feliu,
Lledós Agustí,
Vallribera Adelina,
MorenoMañas Marcial
Publication year - 2008
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200800762
Subject(s) - chemistry , oniom , cyclopropanation , enthalpy , gibbs free energy , catalysis , oxazoline , transition state , copper , potential energy surface , computational chemistry , thermodynamics , organic chemistry , molecule , physics
The enantioselectivity in the reaction of [Cu(adam‐box)(CHCO 2 Me)] {adam‐box = 2,2′‐isopropylidenebis[( 4R )‐(1‐adamantyl)‐2‐oxazoline]} with Ph 2 C=CH 2 was analyzed computationally by ONIOM(B3LYP:UFF) calculations. The lack of transition states in the potential‐energy surface precludes the use of conventional approaches and requires the definition of reaction paths in an approximate Gibbs free‐energy surface. The procedure is time consuming and intrinsically less accurate than the usual approaches based on enthalpic energy surfaces, but it produces results in reasonable agreement with experiment, which furthermore allow identification of the key interactions responsible for chiral discrimination.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)