Journal
ORGANIC & BIOMOLECULAR CHEMISTRY
Volume 13, Issue 30, Pages 8251-8260Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5ob00977d
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Funding
- National Natural Science Foundation of China [21173126, 21403123, 21473100]
- Project of Shandong Province Higher Educational Science and Technology Program [J14LC17]
- Doctoral Start-Up Scientific Research Foundation of Qufu Normal University [BSQD2012018]
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Density functional theory (DFT) calculations have been performed to investigate the detailed mechanism of Rh(iii)-catalyzed redox-neutral C-H activation of pyrazolones with PhCCPh. It is found that (1) the methylene C-H activation is prior to the phenyl C-H activation, (2) the N-N bond cleavage is realized via Rh(iii) Rh(i) Rh(iii) rather than via Rh(iii) -> Rh(v) -> Rh(iii). The zwitterionic Rh(i) complex is identified to be a key intermediate in promoting the N-N bond cleavage. (3) Different from the Rh(iii)-catalyzed hydrazine-directed C-H activation for indole synthesis, the rate-determining step of the reaction studied in this work is the Rh(iii) Rh(i) Rhliii) process resulting in the N-N bond cleavage rather than the alkyne insertion step. The present theoretical study provides new insight into the mechanism of the conjugated N-N bond cleavage.
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