A density functional theory study of the nef-isocyanide reaction: Mechanism, influence of parameters and scope

Nicolas Chéron; Laurent El Kaïm; Laurence Grimaud; Paul Fleurat-Lessard

doi:10.1021/jp205909d

A density functional theory study of the nef-isocyanide reaction: Mechanism, influence of parameters and scope

Nicolas Chéron
, Laurent El Kaïm
, Laurence Grimaud
, Paul Fleurat-Lessard

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

Abstract

The Nef reaction between isocyanides and acyl chlorides is studied at the M06-2X/6-311+G(d,p) level of theory in toluene. After proving that the reaction follows a concerted mechanism instead of an addition-elimination path, we study the influences of the solvent, the isocyanide, the acyl moiety and the leaving group on the energy profile of the reaction. The calculated data can be rationalized with the pK_a of the leaving group, or more generally with the population of the oxygen lone pairs of the acyl moiety.

Original language	English
Pages (from-to)	10106-10112
Number of pages	7
Journal	Journal of Physical Chemistry A
Volume	115
Issue number	35
DOIs	https://doi.org/10.1021/jp205909d
Publication status	Published - 8 Sept 2011
Externally published	Yes

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abstract = "The Nef reaction between isocyanides and acyl chlorides is studied at the M06-2X/6-311+G(d,p) level of theory in toluene. After proving that the reaction follows a concerted mechanism instead of an addition-elimination path, we study the influences of the solvent, the isocyanide, the acyl moiety and the leaving group on the energy profile of the reaction. The calculated data can be rationalized with the pKa of the leaving group, or more generally with the population of the oxygen lone pairs of the acyl moiety.",

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T1 - A density functional theory study of the nef-isocyanide reaction

T2 - Mechanism, influence of parameters and scope

AU - Chéron, Nicolas

AU - El Kaïm, Laurent

AU - Grimaud, Laurence

AU - Fleurat-Lessard, Paul

PY - 2011/9/8

Y1 - 2011/9/8

N2 - The Nef reaction between isocyanides and acyl chlorides is studied at the M06-2X/6-311+G(d,p) level of theory in toluene. After proving that the reaction follows a concerted mechanism instead of an addition-elimination path, we study the influences of the solvent, the isocyanide, the acyl moiety and the leaving group on the energy profile of the reaction. The calculated data can be rationalized with the pKa of the leaving group, or more generally with the population of the oxygen lone pairs of the acyl moiety.

AB - The Nef reaction between isocyanides and acyl chlorides is studied at the M06-2X/6-311+G(d,p) level of theory in toluene. After proving that the reaction follows a concerted mechanism instead of an addition-elimination path, we study the influences of the solvent, the isocyanide, the acyl moiety and the leaving group on the energy profile of the reaction. The calculated data can be rationalized with the pKa of the leaving group, or more generally with the population of the oxygen lone pairs of the acyl moiety.

UR - https://www.scopus.com/pages/publications/80052310150

U2 - 10.1021/jp205909d

DO - 10.1021/jp205909d

M3 - Article

AN - SCOPUS:80052310150

SN - 1089-5639

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SP - 10106

EP - 10112

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 35

ER -

A density functional theory study of the nef-isocyanide reaction: Mechanism, influence of parameters and scope

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