Electrophilic activation of CO₂ in cycloaddition reactions towards a nucleophilic carbenoid intermediate: new defying insights from the Molecular Electron Density Theory

详细信息    查看全文

• 作者：Luis R. Domingo ; Mar Ríos-Gutiérrez ; Eduardo Chamorro…
• 关键词：Carbenoid intermediate ; C–C bond formation ; Molecular electron density theory ; Density functional theory calculations ; Electrophilic activation of CO2
• 刊名：Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：136
• 期：1
• 全文大小：963 KB
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Theoretical and Computational Chemistry
  Inorganic Chemistry
  Organic Chemistry
  Physical Chemistry
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1432-2234
• 卷排序：136

文摘

The electrophilic activation of the two C=O double bonds of CO₂ in the cycloaddition reactions involved in the domino reaction between methyl isocyanide, acetylenedicarboxylate and CO₂ yielding a spiro-compound has been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d,p) computational level. The approaching mode of the carbonyl groups of CO₂ and lactone to the high nucleophilic carbenoid intermediate generated in the first reaction of this domino process promotes the C–C bond formation and the subsequent ring closure. MEDT analysis of cycloaddition reactions involved in this domino process enables to understand the molecular mechanism of these [2n + 2n] cycloadditions, which is different from the previously proposed [4π + 2π] cycloadditions derived from the Frontier Molecular Orbital theory.