A potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights
KAUST DepartmentChemical Science Program
Homogeneous Catalysis Laboratory (HCL)
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Permanent link to this recordhttp://hdl.handle.net/10754/604353
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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 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.
CitationA potential role of substrate as a base for deprotonation pathway in Rh-catalysed C-H amination of heteroArenes: DFT insights 2016 Dalton Trans.
SponsorsThis 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.
PublisherRoyal Society of Chemistry (RSC)
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