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DFT Mechanistic Investigation of the Gold(I)‐Catalyzed Synthesis of Azepino[1,2‐ a ]indoles
Author(s) -
Giacinto Pietro,
Cera Gianpiero,
Bottoni Andrea,
Bandini Marco,
Miscione Gian Pietro
Publication year - 2015
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201500429
Subject(s) - carbenoid , intramolecular force , moiety , chemistry , nucleophile , catalysis , combinatorial chemistry , ring (chemistry) , stereochemistry , computational chemistry , medicinal chemistry , organic chemistry , rhodium
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 in situ. 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.