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    A potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights

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    Type
    Article
    Authors
    Ajitha, Manjaly John
    Huang, Kuo-Wei cc
    Kwak, Jaesung
    Kim, Hyun Jin
    Chang, Sukbok
    Jung, Yousung
    KAUST Department
    Chemical Science Program
    Homogeneous Catalysis Laboratory (HCL)
    KAUST Catalysis Center (KCC)
    Physical Science and Engineering (PSE) Division
    Date
    2016
    Permanent link to this record
    http://hdl.handle.net/10754/604353
    
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    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 hetero-aryl substrate (2-phenylpyridine) using phenyl azide as 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 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 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 base, as disclosed here, can potentially have broader mechanistic implications for the development of reaction conditions of transition metal catalysed reactions.
    Citation
    A potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights 2016 Dalton Trans.
    Sponsors
    This work was supported by the National Research Foundation of Korea Grant (NRF-2015R1A2A1A15055539) funded by Korean Government. The generous support from computation facilities at the KAUST IT and Supercomputing Lab as well as KISTI is also acknowledged.
    Publisher
    Royal Society of Chemistry (RSC)
    Journal
    Dalton Trans.
    DOI
    10.1039/C6DT00686H
    PubMed ID
    27071025
    Additional Links
    http://pubs.rsc.org/en/Content/ArticleLanding/2016/DT/C6DT00686H
    ae974a485f413a2113503eed53cd6c53
    10.1039/C6DT00686H
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

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