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
收藏
页码：2480 / 2484
页数：5
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