%0 Journal Article %1 hlwoodcock:Bernardi1997b %A Bernardi, F. %A Bottoni, A. %A Miscione, G. P. %D 1997 %J JOURNAL OF THE AMERICAN CHEMICAL SOCIETY %K bibtex-import %N 50 %P 12300--12305 %T A DFT study of the Simmons-Smith cyclopropanation reaction %V 119 %X In this paper we have used a DFT (B3LYP) approach to investigate the potential energy surface for the reaction between ethylene and (chloromethyl)zinc chloride (ClCH2ZnCl), which represent a model system for the Simmons-Smith cyclopropanation reaction. Two reaction channels have been found: one leads to the cyclopropane product (addition channel) and the other to the propene product (insertion channel). The addition reaction has an activation energy of 24.7 kcal mol(-1) and, as experimentally found, is favored with respect to the insertion, which is characterized by a larger activation energy (36.0 kcal mol(-1)). The addition transition state corresponds to a three-centered structure which explains the stereochemical features which have been experimentally observed for this reaction. A simple diabatic model is used to rationalize the reactivity pattern that characterizes the Simmons-Smith cyclopropanation and the different behavior observed for the reaction between singlet methylene (CH2)-C-1 and olefins.

@article{hlwoodcock:Bernardi1997b, abstract = {In this paper we have used a DFT (B3LYP) approach to investigate the potential energy surface for the reaction between ethylene and (chloromethyl)zinc chloride (ClCH2ZnCl), which represent a model system for the Simmons-Smith cyclopropanation reaction. Two reaction channels have been found: one leads to the cyclopropane product (addition channel) and the other to the propene product (insertion channel). The addition reaction has an activation energy of 24.7 kcal mol(-1) and, as experimentally found, is favored with respect to the insertion, which is characterized by a larger activation energy (36.0 kcal mol(-1)). The addition transition state corresponds to a three-centered structure which explains the stereochemical features which have been experimentally observed for this reaction. A simple diabatic model is used to rationalize the reactivity pattern that characterizes the Simmons-Smith cyclopropanation and the different behavior observed for the reaction between singlet methylene (CH2)-C-1 and olefins.}, added-at = {2006-06-16T05:03:46.000+0200}, author = {Bernardi, F. and Bottoni, A. and Miscione, G. P.}, biburl = {https://www.bibsonomy.org/bibtex/205c4edff831a93b5519dea38785f3690/hlwoodcock}, citeulike-article-id = {569649}, interhash = {71b2aeb64d2c9c3ff9d9d4d8f846fca8}, intrahash = {05c4edff831a93b5519dea38785f3690}, journal = {JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, keywords = {bibtex-import}, number = 50, pages = {12300--12305}, priority = {2}, timestamp = {2006-06-16T05:03:46.000+0200}, title = {A DFT study of the Simmons-Smith cyclopropanation reaction}, volume = 119, year = 1997 }