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Issue 27, 2020
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Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map

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Abstract

Generally, N-heterocyclic carbene (NHC) complexed with carbonyl compounds would transform into several important active intermediates, i.e., enolates, Breslow intermediates, or acylazolium intermediates, which act as either a nucleophile (Nu) or an electrophile (E) to react with the other E/Nu partner. Hence, the key to predicting the origin of chemoselectivity is to compute the activity (i.e., electrophilic index ω for E and nucleophilic index N for Nu) and stability of the intermediates and products, which are suggested in a general mechanistic map of these reactions. To support this point, we selected and studied different cases of the NHC-catalyzed reactions of carbonyl compounds in the presence of a base and/or an oxidant, in which multiple possible pathways involving acylazolium, enolate, Breslow, and α,β-unsaturated acylazolium intermediates were proposed and a novel index ω + N of the E and Nu partners was employed to exactly predict the energy barrier of the chemoselective step in theory. This work provides a guide for determining the general principle behind organocatalytic reactions with various chemoselectivities, and suggests a general application of the reaction index in predicting the chemoselectivity of the nucleophilic and electrophilic reactions.

Graphical abstract: Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map

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Supplementary files

Article information


Submitted
27 Mar 2020
Accepted
20 Jun 2020
First published
22 Jun 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 7214-7225
Article type
Edge Article

Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds: a general mechanistic map

X. Li, J. Xu, S. Li, L. Qu, Z. Li, Y. R. Chi, D. Wei and Y. Lan, Chem. Sci., 2020, 11, 7214
DOI: 10.1039/D0SC01793K

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