Computational S<sub>N</sub>2‐Type Mechanism for the Difluoromethylation of Lithium Enolate with Fluoroform through Bimetallic C−F Bond Dual Activation
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- Kazuya Honda
- Department of Applied Chemistry Tokyo Institute of Technology Tokyo 152-8552 Japan
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- Travis V. Harris
- Fukui Institute for Fundamental Chemistry Kyoto University Kyoto 606-8103 Japan
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- Miho Hatanaka
- Fukui Institute for Fundamental Chemistry Kyoto University Kyoto 606-8103 Japan
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- Keiji Morokuma
- Fukui Institute for Fundamental Chemistry Kyoto University Kyoto 606-8103 Japan
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- Koichi Mikami
- Department of Applied Chemistry Tokyo Institute of Technology Tokyo 152-8552 Japan
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説明
<jats:title>Abstract</jats:title><jats:p>The reaction mechanism for difluoromethylation of lithium enolates with fluoroform was analyzed computationally (DFT calculations with the artificial force induced reaction (AFIR) method and solvation model based on density (SMD) solvation model (THF)), showing an S<jats:sub>N</jats:sub>2‐type carbon–carbon bond formation; the “bimetallic” lithium enolate and lithium trifluoromethyl carbenoid exert the C−F bond “dual” activation, in contrast to the monometallic butterfly‐shaped carbenoid in the Simmons–Smith reaction. Lithium enolates, generated by the reaction of 2 equiv. of lithium hexamethyldisilazide (rather than 1 or 3 equiv.) with the cheap difluoromethylating species fluoroform, are the most useful alkali metal intermediates for the synthesis of pharmaceutically important α‐difluoromethylated carbonyl products.</jats:p>
収録刊行物
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- Chemistry – A European Journal
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Chemistry – A European Journal 22 (26), 8796-8800, 2016-05-20
Wiley
