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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dc.contributor.authorAjitha, Manjaly J.ko
dc.contributor.authorHuang, Kuo-Weiko
dc.contributor.authorKwak, Jaesungko
dc.contributor.authorKim, Hyun Jinko
dc.contributor.authorChang, Sukbokko
dc.contributor.authorJung, Yousungko
dc.date.accessioned2016-07-06T04:26:59Z-
dc.date.available2016-07-06T04:26:59Z-
dc.date.created2016-06-08-
dc.date.created2016-06-08-
dc.date.issued2016-05-
dc.identifier.citationDALTON TRANSACTIONS, v.45, no.19, pp.7980 - 7985-
dc.identifier.issn1477-9226-
dc.identifier.urihttp://hdl.handle.net/10203/209567-
dc.description.abstractThe 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.languageEnglish-
dc.publisherROYAL SOC CHEMISTRY-
dc.titleA potential role of a substrate as a base for the deprotonation pathway in Rh-catalysed C-H amination of heteroarenes: DFT insights-
dc.typeArticle-
dc.identifier.wosid000375605900006-
dc.identifier.scopusid2-s2.0-84971330659-
dc.type.rimsART-
dc.citation.volume45-
dc.citation.issue19-
dc.citation.beginningpage7980-
dc.citation.endingpage7985-
dc.citation.publicationnameDALTON TRANSACTIONS-
dc.identifier.doi10.1039/c6dt00686h-
dc.contributor.localauthorChang, Sukbok-
dc.contributor.localauthorJung, Yousung-
dc.contributor.nonIdAuthorAjitha, Manjaly J.-
dc.contributor.nonIdAuthorHuang, Kuo-Wei-
dc.description.isOpenAccessN-
dc.type.journalArticleArticle-
dc.subject.keywordPlusASSISTED PROTON-TRANSFER-
dc.subject.keywordPlusBOND ACTIVATION-
dc.subject.keywordPlusNITRENE COMPLEXES-
dc.subject.keywordPlusIMIDO COMPLEXES-
dc.subject.keywordPlusNITROGEN-SOURCE-
dc.subject.keywordPlusAZIDE COMPOUNDS-
dc.subject.keywordPlusORGANIC AZIDES-
dc.subject.keywordPlusARENES-
dc.subject.keywordPlusFUNCTIONALIZATION-
dc.subject.keywordPlusAMIDATION-
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