Unified metal-free intermolecular Heck-type sulfonylation, cyanation, amination, amidation of alkenes by thianthrenation

Ming-Shang Liu; Hai-Wu Du; Huan Meng; Ying Xie; Wei Shu

doi:10.1038/s41467-024-44746-w

Unified metal-free intermolecular Heck-type sulfonylation, cyanation, amination, amidation of alkenes by thianthrenation

Nat Commun. 2024 Jan 15;15(1):529. doi: 10.1038/s41467-024-44746-w.

Authors

Ming-Shang Liu¹, Hai-Wu Du^{1

2}, Huan Meng¹, Ying Xie³, Wei Shu^{4

5

6}

Affiliations

¹ Shenzhen Grubbs Institute and Department of Chemistry, Guangming Advanced Research Institute, Southern University of Science and Technology, 518055, Shenzhen, Guangdong, P. R. China.
² State Key Laboratory of Elemento-Organic Chemistry, Nankai University, 300071, Tianjin, P. R. China.
³ College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, 643000, Zigong, P. R. China.
⁴ Shenzhen Grubbs Institute and Department of Chemistry, Guangming Advanced Research Institute, Southern University of Science and Technology, 518055, Shenzhen, Guangdong, P. R. China. shuw@sustech.edu.cn.
⁵ State Key Laboratory of Elemento-Organic Chemistry, Nankai University, 300071, Tianjin, P. R. China. shuw@sustech.edu.cn.
⁶ College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, 643000, Zigong, P. R. China. shuw@sustech.edu.cn.

Abstract

Direct and site-selective C-H functionalization of alkenes under environmentally benign conditions represents a useful and attractive yet challenging transformation to access value-added molecules. Herein, a unified protocol for a variety of intermolecular Heck-type functionalizations of C_sp2-H bond of alkenes has been developed by thianthrenation. The reaction features metal-free and operationally simple conditions for exclusive cine-selective C-H functionalization of aliphatic and aryl alkenes to forge C-C, C-N, C-P, and C-S bonds at room temperature, providing a general protocol for intermolecular Heck-type reaction of alkenes with nucleophiles (Nu = sulfinates, cyanides, amines, amides). Alkenes undergo cine-sulfonylation, cyanation, amination to afford alkenyl sulfones, alkenyl nitriles and enamines.

Abstract

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