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Title: Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds : a general mechanistic map
Authors: Li, Xue
Xu, Jun
Li, Shi-Jun
Qu, Ling-Bo
Li, Zhongjun
Chi, Robin Yonggui
Wei, Donghui
Lan, Yu
Keywords: Science::Chemistry
Issue Date: 2020
Source: Li, X., Xu, J., Li, S., Qu, L., Li, Z., Chi, R. Y., Wei, D. & Lan, Y. (2020). Prediction of NHC-catalyzed chemoselective functionalizations of carbonyl compounds : a general mechanistic map. Chemical Science, 11(27), 7214-7225.
Journal: Chemical Science
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.
ISSN: 2041-6520
DOI: 10.1039/d0sc01793k
Rights: © 2020 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:SPMS Journal Articles

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