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羰基化合物中亲电性的定义是什么。

What defines electrophilicity in carbonyl compounds.

作者信息

Bickelhaupt F Matthias, Fernández Israel

机构信息

Department of Chemistry and Pharmaceutical Sciences, AIMMS, Vrije Universiteit Amsterdam The Netherlands

Institute for Molecules and Materials (IMM), Radboud University Nijmegen The Netherlands.

出版信息

Chem Sci. 2024 Feb 6;15(11):3980-3987. doi: 10.1039/d3sc05595g. eCollection 2024 Mar 13.

DOI:10.1039/d3sc05595g
PMID:38487236
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10935700/
Abstract

The origin of the electrophilicity of a series of cyclohexanones and benzaldehydes is investigated using the activation strain model and quantitative Kohn-Sham molecular orbital (MO) theory. We find that this electrophilicity is mainly determined by the electrostatic attractions between the carbonyl compound and the nucleophile (cyanide) along the entire reaction coordinate. Donor-acceptor frontier molecular orbital interactions, on which the current rationale behind electrophilicity trends is based, appear to have little or no significant influence on the reactivity of these carbonyl compounds.

摘要

利用活化应变模型和定量的含时密度泛函理论，研究了一系列环己酮和苯甲醛亲电性的来源。我们发现，这种亲电性主要由羰基化合物与亲核试剂（氰化物）在整个反应坐标上的静电吸引作用决定。目前亲电性趋势背后的理论基础——给体-受体前线分子轨道相互作用，似乎对这些羰基化合物的反应活性几乎没有显著影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/afbac10b0a0d/d3sc05595g-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/20202e15181c/d3sc05595g-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/6cbfc8391cec/d3sc05595g-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/afbac10b0a0d/d3sc05595g-f8.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/20202e15181c/d3sc05595g-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/83c86ae54a23/d3sc05595g-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/89e7c13c16c3/d3sc05595g-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/a3e165d11cfd/d3sc05595g-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/1a77419d79fa/d3sc05595g-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/1f1ff772cacb/d3sc05595g-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/6cbfc8391cec/d3sc05595g-f7.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b550/10935700/afbac10b0a0d/d3sc05595g-f8.jpg

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