Synthesis of Substituted Pyrroles via Copper-Catalyzed Cyclization of Ethyl Allenoates with Activated Isocyanides

Kui Lu; Fang Ding; Long Qin; Xiaoliang Jia; Chuanming Xu; Xia Zhao; Qingwei Yao; Peng Yu

doi:10.1002/asia.201600761

Synthesis of Substituted Pyrroles via Copper-Catalyzed Cyclization of Ethyl Allenoates with Activated Isocyanides

Chem Asian J. 2016 Aug 5;11(15):2121-5. doi: 10.1002/asia.201600761. Epub 2016 Jul 13.

Authors

Kui Lu¹, Fang Ding², Long Qin², Xiaoliang Jia², Chuanming Xu², Xia Zhao³, Qingwei Yao⁴, Peng Yu⁵

Affiliations

¹ China International Science and Technology Cooperation Base of Food Nutrition/Safety and Medicinal Chemistry, Sino-French Joint Lab of Food Nutrition/Safety and Medicinal Chemistry, Key Laboratory of Industrial Microbiology of Ministry of Education, Tianjin Key Laboratory of Industry Microbiology, College of Biotechnology, Tianjin University of Science & Technology, Tianjin, 300457, China. lukui@tust.edu.cn.
² China International Science and Technology Cooperation Base of Food Nutrition/Safety and Medicinal Chemistry, Sino-French Joint Lab of Food Nutrition/Safety and Medicinal Chemistry, Key Laboratory of Industrial Microbiology of Ministry of Education, Tianjin Key Laboratory of Industry Microbiology, College of Biotechnology, Tianjin University of Science & Technology, Tianjin, 300457, China.
³ College of Chemistry, Tianjin Normal University, Tianjin, 300387, China.
⁴ Sphinx Scientific Laboratory Corporation, 2402 Heights Ave., Cody, Wyoming, 82414, USA.
⁵ China International Science and Technology Cooperation Base of Food Nutrition/Safety and Medicinal Chemistry, Sino-French Joint Lab of Food Nutrition/Safety and Medicinal Chemistry, Key Laboratory of Industrial Microbiology of Ministry of Education, Tianjin Key Laboratory of Industry Microbiology, College of Biotechnology, Tianjin University of Science & Technology, Tianjin, 300457, China. yupeng@tust.edu.cn.

PMID: 27348611
DOI: 10.1002/asia.201600761

Abstract

A new method for the synthesis of di- and trisubstituted pyrroles via copper-catalyzed cyclization of ethyl allenoates with activated isocyanides has been developed. In contrast to related annulation reactions previously reported, this new process features a skeletal rearrangement in which the aryl sulfonyl moiety, which functions as the electron-withdrawing group in the α-carbon of the isocyanide, was found to migrate to the γ-carbon of the starting allenoate in the final product for the first time.

Keywords: allenoates; copper; cyclization; isocyanides; pyrrole synthesis.