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Selective ortho C−H Cyanoalkylation of (Diacetoxyiodo)arenes through [3,3]‐Sigmatropic Rearrangement
Author(s) -
Tian Junsong,
Luo Fan,
Zhang Chaoshen,
Huang Xin,
Zhang Yage,
Zhang Lei,
Kong Lichun,
Hu Xiaochun,
Wang ZhiXiang,
Peng Bo
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201803455
Subject(s) - nitrile , aryl , sigmatropic reaction , chemistry , ketenimine , functional group , iodide , catalysis , medicinal chemistry , transformation (genetics) , combinatorial chemistry , organic chemistry , alkyl , biochemistry , gene , polymer
We herein report a robust catalyst‐free cross‐coupling between ArI(OAc) 2 and α‐stannyl nitriles, aided by TMSOTf. The transformation introduces a cyanoalkyl group to the ortho position of ArI(OAc) 2 and simultaneously reduces the aryl iodine(III) to iodide, thus providing α‐(2‐iodoaryl) nitrile as the product. This transformation could be completed within 5 min at −78 °C and features superb functional‐group tolerance and efficient scalability. DFT calculations indicate that the formation of a ketenimine(aryl)iodonium intermediate and subsequent [3,3]‐sigmatropic rearrangement are involved as key steps.