[3, 3]‐Sigmatropic Rearrangement of Aryl Fluoroalkyl Sulfoxides with Alkyl Nitriles. Issue 2 (19th December 2019)

• Record Type: Journal Article
• Authors: Hu, Mengjie; He, Jia‐Ni; Liu, Yanping; Dong, Taotao; Chen, Mengyuan; Yan, Chao; Ye, Yulu; Peng, Bo
• Is Part Of: European journal of organic chemistry. Issue 2(2020)
• Page Start: 193
• Page End: 197
• Publication Date: 2019-12-19
• Subjects: C‐H functionalization -- Difluoromethylthio group -- Sigmatropic rearrangement -- Sulfoxides -- Synthetic methods; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201901577
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : Herein we report the ortho ‐cyanoalkylation of aryl fluoroalkyl sulfoxides with alkyl nitriles. The reaction proceeds through an "assembly/deprotonation" triggered [3, 3]‐rearrangement and allows the incorporation of two valuable functional groups including the cyano group and difluoromethylthio group into arenes. As a consequence, a wide range of ortho ‐cyanoalkylated difluoromethylthio arenes were produced with high efficiency under mild and environmentally friendly conditions. Remarkably, the reaction proceeds smoothly with the electron‐donating group substituted arenes which can be challenging to the reaction of non‐fluoroalkyl sulfoxides. This beneficial effect can be attributed to the unique electronegativity of fluoroalkyl substituents. Abstract : This work describes the ortho ‐cyanoalkylation of aryl fluoroalkyl sulfoxides with alkyl nitriles through an "assembly/deprotonation"‐triggered [3, 3]‐rearrangement, which enables the installation of two valuable functional groups including the cyano group and difluoromethylthio group into arenes.