Dividing a complex reaction involving a hypervalent iodine reagent into three limiting mechanisms by <i>ab initio</i> molecular dynamics

DOI Web Site Web Site 被引用文献2件
  • Oliver Sala
    ETH Zurich, Laboratorium für Physikalische Chemie Vladimir–Prelog–Weg 2 8093 Zurich Switzerland
  • Hans Peter Lüthi
    ETH Zurich, Laboratorium für Physikalische Chemie Vladimir–Prelog–Weg 2 8093 Zurich Switzerland
  • Antonio Togni
    ETH Zurich, Laboratorium für Physikalische Chemie Vladimir–Prelog–Weg 2 8093 Zurich Switzerland
  • Marcella Iannuzzi
    University of Zurich Department of Chemistry Winterthurerstrasse 190 8057 Zurich Switzerland
  • Jürg Hutter
    University of Zurich Department of Chemistry Winterthurerstrasse 190 8057 Zurich Switzerland

書誌事項

公開日
2015-03-12
権利情報
  • http://onlinelibrary.wiley.com/termsAndConditions#vor
DOI
  • 10.1002/jcc.23857
公開者
Wiley

この論文をさがす

説明

<jats:p>The electrophilic <jats:italic>N</jats:italic>‐trifluoromethylation of MeCN with a hypervalent iodine reagent to form a nitrilium ion, that is rapidly trapped by an azole nucleophile, is thought to occur via reductive elimination (RE). A recent study showed that, depending on the solvent representation, the S<jats:sub><jats:italic>N</jats:italic></jats:sub>2 is favoured to a different extent over the RE. However, there is a discriminative solvent effect present, which calls for a statistical mechanics approach to fully account for the entropic contributions. In this study, we perform metadynamic simulations for two trifluoromethylation reactions (with <jats:italic>N</jats:italic>‐ and <jats:italic>S</jats:italic>‐nucleophiles), showing that the RE mechanism is always favoured in MeCN solution. These computations also indicate that a radical mechanism (single electron transfer) may play an important role. The computational protocol based on accelerated molecular dynamics for the exploration of the free energy surface is transferable and will be applied to similar reactions to investigate other electrophiles on the reagent. Based on the activation parameters determined, this approach also gives insight into the mechanistic details of the trifluoromethylation and shows that these commonly known mechanisms mark the limits within which the reaction proceeds. © 2015 Wiley Periodicals, Inc.</jats:p>

収録刊行物

被引用文献 (2)*注記

もっと見る

詳細情報 詳細情報について

問題の指摘

ページトップへ