Rhodium(II)-Catalyzed Intramolecular Annulation of 1-Sulfonyl-1,2,3-Triazoles with Pyrrole and Indole Rings: Facile Synthesis of N-Bridgehead Azepine Skeletons

• Published in: Angewandte Chemie International Edition Vol. 53; no. 20; pp. 5142 - 5146
• Main Authors: Yang, Jin-Ming, Zhu, Cheng-Zhi, Tang, Xiang-Ying, Shi, Min
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 12-05-2014; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: annulation; Azepines - chemistry; Catalysis; Chemical reactions; heterocycles; Indoles; Pharmaceutical industry; reaction mechanisms; Rhodium; Rhodium - chemistry; synthetic methods; Triazoles - chemistry; reaction mechanisms; annulation; heterocycles; synthetic methods; rhodium
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201400881

A convenient and efficient synthetic method has been developed to construct highly functionalized N‐bridgehead azepine skeletons, which are of great importance in biological and pharmaceutical industry. The reaction proceeds through a rhodium(II) azavinyl carbene intermediate, which initiated the intramolecular CH functionalization with pyrrolyl and indolyl rings. A variety of azepine derivatives were obtained in moderate to good yields under mild reaction conditions with high chemoselectivity. Several interesting derivatizations of the resulting products demonstrate that this method is synthetically valuable and useful.
Heads up: A convenient and efficient synthetic method of highly functionalized N‐bridgehead azepine skeletons was developed using a rhodium(II)‐catalyzed intramolecular annulation of pyrrolyl and indolyl triazoles. Several interesting transformations of the products into poly‐heterocyclic products and the reaction mechanism are disclosed. Ts=4‐toluenesulfonyl.