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분자활성 촉매반응 연구단
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A potential role of a substrate as a base for the deprotonation pathway in Rh-catalysed C-H amination of heteroarenes: DFT insights

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Title
A potential role of a substrate as a base for the deprotonation pathway in Rh-catalysed C-H amination of heteroarenes: DFT insights
Author(s)
Ajitha M.J.; Huang K.-W.; Jaesung Kwak; Hyun Jin Kim; Sukbok Chang; Jung Y.
Publication Date
2016-05
Journal
DALTON TRANSACTIONS, v.45, no.19, pp.7980 - 7985
Publisher
ROYAL SOC CHEMISTRY
Abstract
The possibility of direct introduction of a new functionality through C-H bond activation is an attractive strategy in covalent synthesis. Here, we investigated the mechanism of Rh-catalysed C-H amination of the heteroaryl substrate (2-phenylpyridine) using phenyl azide as a nitrogen source by density functional theory (DFT). For the deprotocyclometallation and protodecyclometallation processes of the title reaction, we propose a stepwise base-assisted mechanism (pathway I) instead of the previously reported concerted mechanism (pathway II). In the new mechanism proposed here, 2-phenylpyridine acts as a base in the initial deprotonation step (C-H bond cleavage) and transports the proton towards the final protonation step. In fact, the N-H bond of the strong conjugate acid (formed during the initial C-H bond cleavage) considered in pathway I (viaTS4) is more acidic than the C-H bond of the neutral substrate considered in pathway II (viaTS5). The higher activation barrier of TS5 mainly originates from the ring strain of the four-membered cyclic transition state. The vital role of the base, as disclosed here, can potentially have broader mechanistic implications for the development of reaction conditions of transition metal-catalysed reactions. © 2016 The Royal Society of Chemistry
URI
https://pr.ibs.re.kr/handle/8788114/2639
ISSN
1477-9226
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
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