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A radical-mediated hetaryl functionalization of nonactivated alkenes through distal ipso -migration of O- or S-containing hetaryls was developed. Furyl, benzofuryl, thienyl, and benzothienyl groups showed satisfactory migratory abilities. A variety of heteroatom-centered radicals, including azido, trifluoromethylsulfanyl, and silyl radicals readily trigger the migration cascade, and a new C–heteroatom and C–C bond are concomitantly constructed in the reaction. This method provides an efficient approach to the synthesis of high-valued complex O- or S-hetaryl compounds. [ABSTRACT FROM AUTHOR]

Free radical mediated alkylation of alkenes is a challenging and largely unmet goal. Disclosed here is a conceptually novel "polarity umpolung" strategy for radical alkylation of alkenes using a portfolio of easily accessed, difunctional alkylating reagents. This strategy is achieved by substituting inherently nucleophilic alkyl radicals with electrophilic sulfone‐bearing surrogates, thus inverting the usual mode of reactivity. Along with alkylation, either an heteroaryl or oximino group is concurrently incorporated into the alkenes by a consecutive docking and migration process, leading to valuable products. The reaction displays a broad functional‐group tolerance under mild reaction conditions. The protocol opens new vistas for the late‐stage modification of complex natural products and drug molecules containing alkene moieties. [ABSTRACT FROM AUTHOR]

Regioselective incorporation of a particular functional group into aliphatic sites by direct activation of unreactive C−H bonds is of great synthetic value. Despite advances in radical‐mediated functionalization of C(sp3)−H bonds by a hydrogen‐atom transfer process, the site‐selective vinylation of remote C(sp3)−H bonds still remains underexplored. Reported herein is a new protocol for the regioselective vinylation of unactivated C(sp3)−H bonds. The remote C(sp3)−H activation is promoted by a C‐centered radical instead of the commonly used N and O radicals. The reaction possesses high product diversity and synthetic efficiency, furnishing a plethora of synthetically valuable E alkenes bearing tri‐/di‐/mono‐fluoromethyl and perfluoroalkyl groups. Give and take: Regioselective incorporation of a particular functional group into aliphatic sites by direct activation of unreactive C−H bonds remains challenging. Herein a new protocol for the regioselective vinylation of unactivated C(sp3)−H bonds is reported. The activation of a remote C(sp3)−H bond is promoted by a C‐centered radical instead of the commonly used N and O radicals. [ABSTRACT FROM AUTHOR]

Abstract: Reported for the first time is a tertiary‐alcohol‐guided heteroarylation of remote C(sp3)−H bonds. The mild and direct generation of alkoxyl radicals from alcohols is enabled by visible‐light photocatalysis. A remote hydrogen atom and heteroaryl migration sequence are involved in the reaction. Many sensitive groups remain intact in the reaction, thus illustrating wide functional‐group compatibility. This protocol provides a practical strategy for the late‐stage modification of alkyl ketones. [ABSTRACT FROM AUTHOR]

Disclosed herein is a novel, redox-neutral protocol for the visible-light-induced radical alkynylation of unactivated olefins. The intramolecular migration of an alkynyl group, by cleaving an inert C−C σ bond, is realized for the first time. A wide range of synthetically useful trifluoroethylated linear alkynes are readily obtained under mild reaction conditions. [ABSTRACT FROM AUTHOR]

Chen Zhu: (left) received his B.S. degree from Xiamen University in 2003 under the supervision of Prof. Pei-Qiang Huang, and his Ph.D. degree from the Shanghai Institute of Organic Chemistry in 2008 under the supervision of Prof. Guo-Qiang Lin. After postdoctoral research at -Gakushuin University, Japan with Prof. Takahiko Akiyama, he moved to the University of Texas Southwestern Medical Center, working as a postdoctoral fellow with Prof. John R. Falck and Prof. Chuo Chen. He was appointed as a professor at Soochow University, China in December 2013. He is currently the Head of the Organic Chemistry Department at Soochow University. His current research interests include radical-mediated transformations, in particular radical -rearrangements, and their applications in the construction of natural products and biologically active compounds. Xin-Yuan Liu (right) obtained his B.S. degree from Anhui Normal University (AHNU) in 2001. He continued his research studies at both the Shanghai Institute of Organic Chemistry (SIOC), CAS and AHNU under the joint supervision of Prof. Dr. Shizheng Zhu and Prof. Dr. Shaowu Wang, obtaining his master's degree in 2004. After a one-year stint in Prof. Gang Zhao's laboratory at SIOC, he joined Prof. Dr. Chi-Ming Che's group at The University of Hong Kong (HKU) and earned his Ph.D. degree in 2010. He subsequently undertook postdoctoral studies in Prof. Che's group at HKU and in Prof. Carlos F. Barbas III's group at The Scripps Research Institute. At the end of 2012, he began his independent academic career at the Southern University of Science and Technology (SUSTech) and was promoted to a tenured Full Professor of SUSTech in 2018. His research interests are directed towards the design of novel chiral anionic ligands to solve radical-involved asymmetric reactions. [ABSTRACT FROM AUTHOR]