DC Field | Value | Language |
---|---|---|
dc.contributor.author | Ajitha, Manjaly J. | ko |
dc.contributor.author | Huang, Kuo-Wei | ko |
dc.contributor.author | Kwak, Jaesung | ko |
dc.contributor.author | Kim, Hyun Jin | ko |
dc.contributor.author | Chang, Sukbok | ko |
dc.contributor.author | Jung, Yousung | ko |
dc.date.accessioned | 2016-07-06T04:26:59Z | - |
dc.date.available | 2016-07-06T04:26:59Z | - |
dc.date.created | 2016-06-08 | - |
dc.date.created | 2016-06-08 | - |
dc.date.issued | 2016-05 | - |
dc.identifier.citation | DALTON TRANSACTIONS, v.45, no.19, pp.7980 - 7985 | - |
dc.identifier.issn | 1477-9226 | - |
dc.identifier.uri | http://hdl.handle.net/10203/209567 | - |
dc.description.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 (via TS4) is more acidic than the C-H bond of the neutral substrate considered in pathway II (via TS5). 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 | - |
dc.language | English | - |
dc.publisher | ROYAL SOC CHEMISTRY | - |
dc.title | A potential role of a substrate as a base for the deprotonation pathway in Rh-catalysed C-H amination of heteroarenes: DFT insights | - |
dc.type | Article | - |
dc.identifier.wosid | 000375605900006 | - |
dc.identifier.scopusid | 2-s2.0-84971330659 | - |
dc.type.rims | ART | - |
dc.citation.volume | 45 | - |
dc.citation.issue | 19 | - |
dc.citation.beginningpage | 7980 | - |
dc.citation.endingpage | 7985 | - |
dc.citation.publicationname | DALTON TRANSACTIONS | - |
dc.identifier.doi | 10.1039/c6dt00686h | - |
dc.contributor.localauthor | Chang, Sukbok | - |
dc.contributor.localauthor | Jung, Yousung | - |
dc.contributor.nonIdAuthor | Ajitha, Manjaly J. | - |
dc.contributor.nonIdAuthor | Huang, Kuo-Wei | - |
dc.description.isOpenAccess | N | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | ASSISTED PROTON-TRANSFER | - |
dc.subject.keywordPlus | BOND ACTIVATION | - |
dc.subject.keywordPlus | NITRENE COMPLEXES | - |
dc.subject.keywordPlus | IMIDO COMPLEXES | - |
dc.subject.keywordPlus | NITROGEN-SOURCE | - |
dc.subject.keywordPlus | AZIDE COMPOUNDS | - |
dc.subject.keywordPlus | ORGANIC AZIDES | - |
dc.subject.keywordPlus | ARENES | - |
dc.subject.keywordPlus | FUNCTIONALIZATION | - |
dc.subject.keywordPlus | AMIDATION | - |
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