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

共 46 条

[1] Targeted Regulation of PI3K/Akt/mTOR/NF-κB Signaling by Indole Compounds and their Derivatives: Mechanistic Details and Biological Implications for Cancer Therapy [J].

Ahmad, Aamir ;

Biersack, Bernhard ;

Li, Yiwei ;

Kong, Dejuan ;

Bao, Bin ;

Schobert, Rainer ;

Padhye, Subhash B. ;

Sarkar, Fazlul H. .

ANTI-CANCER AGENTS IN MEDICINAL CHEMISTRY, 2013, 13 (07) :1002-1013

[2]

Andzelm J., 1984, GAUSSIAN BASIS SETS

[3] Antioxidant Activities of Retinoidal Benzimidazole Or Indole Derivatives in In Vitro Model Systems [J].

Ates-Alagoz, Zeynep .

CURRENT MEDICINAL CHEMISTRY, 2013, 20 (36) :4633-4639

[4] Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model [J].

Barone, V ;

Cossi, M .

JOURNAL OF PHYSICAL CHEMISTRY A, 1998, 102 (11) :1995-2001

[5] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[6] Indole Compounds Against Breast Cancer: Recent Developments [J].

Biersack, Bernhard ;

Schobert, Rainer .

CURRENT DRUG TARGETS, 2012, 13 (14) :1705-1719

[7]

Biswal S., 2012, ASIAN J PHARM CLIN R, V5, P1

[8] Rhodium(III)-Catalyzed Hydrazine-Directed C-H Activation for Indole Synthesis: Mechanism and Role of Internal Oxidant Probed by DFT Studies [J].

Chen, Wen-Jie ;

Lin, Zhenyang .

ORGANOMETALLICS, 2015, 34 (01) :309-318

[9] Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model [J].

Cossi, M ;

Rega, N ;

Scalmani, G ;

Barone, V .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 2003, 24 (06) :669-681

[10] A SET OF F-POLARIZATION FUNCTIONS FOR PSEUDO-POTENTIAL BASIS-SETS OF THE TRANSITION-METALS SC-CU, Y-AG AND LA-AU [J].

EHLERS, AW ;

BOHME, M ;

DAPPRICH, S ;

GOBBI, A ;

HOLLWARTH, A ;

JONAS, V ;

KOHLER, KF ;

STEGMANN, R ;

VELDKAMP, A ;

FRENKING, G .

CHEMICAL PHYSICS LETTERS, 1993, 208 (1-2) :111-114

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