Rh-Catalyzed [2,3]-Sigmatropic Rearrangement of Alkynyl Carbenes with Allyl Sulfides to Access Sulfide-Substituted 1,5-Enynes

Zhongxue Fang; Yu Wang; Yiming Ma; Xinyue Han; Zhaohong Liu; Yongquan Ning

doi:10.1021/acs.joc.2c02910

Rh-Catalyzed [2,3]-Sigmatropic Rearrangement of Alkynyl Carbenes with Allyl Sulfides to Access Sulfide-Substituted 1,5-Enynes

J Org Chem. 2023 Jul 21;88(14):9677-9685. doi: 10.1021/acs.joc.2c02910. Epub 2023 Jun 30.

Authors

Zhongxue Fang¹, Yu Wang², Yiming Ma¹, Xinyue Han², Zhaohong Liu², Yongquan Ning²

Affiliations

¹ School of Chemistry and Environmental Engineering, Yancheng Teachers University, Yancheng 224007, China.
² Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun 130024, China.

PMID: 37389925
DOI: 10.1021/acs.joc.2c02910

Abstract

This study describes the development of Rh-catalyzed [2,3]-sigmatropic rearrangement of alkynyl carbenes with allyl sulfides. The protocol exhibits equitable functional group tolerance and allows the formation of a variety of synthetically valuable sulfide-substituted 1,5-enyne products. To the best of our knowledge, this is the first example of [2,3]-sigmatropic rearrangement of alkynyl carbenes. DFT analysis supports the involvement of rhodium carbene generation, sulfonium ylides formation, and [2,3]-sigmatropic rearrangement pathway.