Mechanistic insight into conjugated N-N bond cleavage by Rh(iii)-catalyzed redox-neutral C-H activation of pyrazolones

被引：26

作者：

Wu, Weirong ^{[1
,2
]}

Liu, Yuxia ^{[1
]}

Bi, Siwei ^{[1
]}

机构：

[1] Qufu Normal Univ, Coll Chem & Chem Engn, Qufu 273165, Peoples R China

[2] Jining Univ, Key Lab Inorgan Chem Univ Shandong, Dept Chem & Chem Engn, Qufu 273155, Shandong, Peoples R China

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2015年 / 13卷 / 30期

基金：

中国国家自然科学基金;

关键词：

EFFECTIVE CORE POTENTIALS; INDOLE SYNTHESIS; MOLECULAR CALCULATIONS; REGIOSELECTIVE SYNTHESIS; DERIVATIVES; FUNCTIONALIZATION; ANILINES; ARENE; SC;

D O I：

10.1039/c5ob00977d

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

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.

引用

页码：8251 / 8260

页数：10

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