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Mechanistic insight into conjugated N-N bond cleavage by Rh(III)-catalyzed redox-neutral C-H activation of pyrazolones.
Org Biomol Chem. 2015 Aug 14; 13(30):8251-60.OB

Abstract

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 PhC≡CPh. 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) → Rh(III) 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.

Authors+Show Affiliations

College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, P. R. China. siweibi@126.com liuyuxia2008@163.com.No affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

26138233

Citation

Wu, Weirong, et al. "Mechanistic Insight Into Conjugated N-N Bond Cleavage By Rh(III)-catalyzed Redox-neutral C-H Activation of Pyrazolones." Organic & Biomolecular Chemistry, vol. 13, no. 30, 2015, pp. 8251-60.
Wu W, Liu Y, Bi S. Mechanistic insight into conjugated N-N bond cleavage by Rh(III)-catalyzed redox-neutral C-H activation of pyrazolones. Org Biomol Chem. 2015;13(30):8251-60.
Wu, W., Liu, Y., & Bi, S. (2015). Mechanistic insight into conjugated N-N bond cleavage by Rh(III)-catalyzed redox-neutral C-H activation of pyrazolones. Organic & Biomolecular Chemistry, 13(30), 8251-60. https://doi.org/10.1039/c5ob00977d
Wu W, Liu Y, Bi S. Mechanistic Insight Into Conjugated N-N Bond Cleavage By Rh(III)-catalyzed Redox-neutral C-H Activation of Pyrazolones. Org Biomol Chem. 2015 Aug 14;13(30):8251-60. PubMed PMID: 26138233.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Mechanistic insight into conjugated N-N bond cleavage by Rh(III)-catalyzed redox-neutral C-H activation of pyrazolones. AU - Wu,Weirong, AU - Liu,Yuxia, AU - Bi,Siwei, PY - 2015/7/4/entrez PY - 2015/7/4/pubmed PY - 2016/5/18/medline SP - 8251 EP - 60 JF - Organic & biomolecular chemistry JO - Org Biomol Chem VL - 13 IS - 30 N2 - 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 PhC≡CPh. 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) → Rh(III) 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. SN - 1477-0539 UR - https://www.unboundmedicine.com/medline/citation/26138233/Mechanistic_insight_into_conjugated_N_N_bond_cleavage_by_Rh_III__catalyzed_redox_neutral_C_H_activation_of_pyrazolones_ L2 - https://doi.org/10.1039/c5ob00977d DB - PRIME DP - Unbound Medicine ER -