DFT Mechanistic Investigation of the Gold(I)-Catalyzed Synthesis of Azepino[1,2-a]indoles

被引：15

作者：

Giacinto, Pietro ^{[1
]}

Cera, Gianpiero ^{[1
]}

Bottoni, Andrea ^{[1
]}

Bandini, Marco ^{[1
]}

Miscione, Gian Pietro ^{[1
,2
]}

机构：

[1] Univ Bologna, Dept Chem G Ciamician, I-40126 Bologna, Italy

[2] Univ Los Andes, Dept Chem, Bogota, Colombia

来源：

CHEMCATCHEM | 2015年 / 7卷 / 16期

关键词：

density functional calculations; gold; hydrogen bonds; reaction mechanisms; transition states; EFFECTIVE CORE POTENTIALS; GOLD-CATALYZED REACTIONS; N-HETEROCYCLIC CARBENE; MOLECULAR CALCULATIONS; THERMOCHEMICAL KINETICS; DENSITY FUNCTIONALS; INDOLES; AU; PI; CYCLIZATIONS;

D O I：

10.1002/cctc.201500429

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We describe a computational DFT investigation on the mechanism of the one-pot synthesis of azepino-indoles catalyzed by [Au(IPr)Cl]/AgOTf (IPr=1,3-bis(2,6-diisopropylphenyl-imidazol-2-ylidene) by the simultaneous construction of the pyrrolyl and seven-membered rings. The mechanism of the final ring-closing event is elucidated, which reveals the counterion-assisted nucleophilic trapping of the carbonyl moiety by the alkenyl-gold species formed insitu. The computational evidence supports the labeling control experiments and highlights the presence of a cyclopropyl-gold-carbenoid intermediate in the final intramolecular 1,3-hydrogen-shift/skeleton-rearrangement sequence.

引用

页码：2480 / 2484

页数：5

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