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

Luis R. Domingo; Mar Ríos-Gutiérrez; Eduardo Chamorro; Patricia Pérez

doi:10.1007/s00214-016-2022-6

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

Luis R. Domingo, Mar Ríos-Gutiérrez, Eduardo Chamorro, Patricia Pérez

Research output: Contribution to journal › Article › peer-review

7 Citations (Scopus)

Abstract

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.

Original language	English
Article number	1
Journal	Theoretical Chemistry Accounts
Volume	136
Issue number	1
DOIs	https://doi.org/10.1007/s00214-016-2022-6
Publication status	Published - 1 Jan 2017

Keywords

Carbenoid intermediate
C–C bond formation
Density functional theory calculations
Electrophilic activation of CO
Molecular electron density theory

ASJC Scopus subject areas

Physical and Theoretical Chemistry

Access to Document

10.1007/s00214-016-2022-6

Cite this

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

abstract = "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.",

keywords = "Carbenoid intermediate, C–C bond formation, Density functional theory calculations, Electrophilic activation of CO, Molecular electron density theory",

author = "Domingo, {Luis R.} and Mar R{\'i}os-Guti{\'e}rrez and Eduardo Chamorro and Patricia P{\'e}rez",

note = "Funding Information: This work has been supported by the Ministerio de Econom{\'i}a y Competitividad of the Spanish Government, project CTQ2013-45646-P, Fondecyt (Chile) grants 1140341 and 1140343, Millennium Nucleus Chemical Processes and Catalysis (CPC) Project No. 120082 and the Universidad Andr{\'e}s Bello (UNAB) for continuous support through research grants DI-806-15/R and DI-793-15/R. Prof L.R.D. also thanks FONDECYT for continuous support through Cooperaci{\'o}n Internacional. M. R.-G. thanks the Ministerio de Econom{\'i}a y Competitividad for a predoctoral contract co-financed by the European Social Fund (BES-2014-068258). Publisher Copyright: {\textcopyright} 2016, Springer-Verlag Berlin Heidelberg.",

year = "2017",

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Electrophilic activation of CO₂ in cycloaddition reactions towards a nucleophilic carbenoid intermediate: new defying insights from the Molecular Electron Density Theory. / Domingo, Luis R.; Ríos-Gutiérrez, Mar; Chamorro, Eduardo et al.
In: Theoretical Chemistry Accounts, Vol. 136, No. 1, 1, 01.01.2017.

Research output: Contribution to journal › Article › peer-review

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AU - Ríos-Gutiérrez, Mar

AU - Chamorro, Eduardo

AU - Pérez, Patricia

N1 - Funding Information: This work has been supported by the Ministerio de Economía y Competitividad of the Spanish Government, project CTQ2013-45646-P, Fondecyt (Chile) grants 1140341 and 1140343, Millennium Nucleus Chemical Processes and Catalysis (CPC) Project No. 120082 and the Universidad Andrés Bello (UNAB) for continuous support through research grants DI-806-15/R and DI-793-15/R. Prof L.R.D. also thanks FONDECYT for continuous support through Cooperación Internacional. M. R.-G. thanks the Ministerio de Economía y Competitividad for a predoctoral contract co-financed by the European Social Fund (BES-2014-068258). Publisher Copyright: © 2016, Springer-Verlag Berlin Heidelberg.

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N2 - 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.

AB - 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.

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KW - Density functional theory calculations

KW - Electrophilic activation of CO

KW - Molecular electron density theory

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