Radical-triggered translocation of C-C double bond and functional group.

Autor: Wang S; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China., Luo X; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China., Wang Y; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China., Liu Z; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China., Yu Y; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China., Wang X; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China., Ren D; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China., Wang P; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China., Chen YH; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China., Qi X; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China. qi7xiaotian@whu.edu.cn.; State Key Laboratory of Power Grid Environmental Protection, School of Electrical Engineering and Automation, Wuhan University, Wuhan, P. R. China. qi7xiaotian@whu.edu.cn., Yi H; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China. hong.yi@whu.edu.cn., Lei A; Institute for Advanced Studies (IAS), College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, P. R. China. aiwenlei@whu.edu.cn.; State Key Laboratory of Power Grid Environmental Protection, School of Electrical Engineering and Automation, Wuhan University, Wuhan, P. R. China. aiwenlei@whu.edu.cn.; National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang, P. R. China. aiwenlei@whu.edu.cn.
Jazyk: angličtina
Zdroj: Nature chemistry [Nat Chem] 2024 Oct; Vol. 16 (10), pp. 1621-1629. Date of Electronic Publication: 2024 Sep 09.
DOI: 10.1038/s41557-024-01633-7
Abstrakt: Multi-site functionalization of molecules provides a potent approach to accessing intricate compounds. However, simultaneous functionalization of the reactive site and the inert remote C(sp 3 )-H poses a formidable challenge, as chemical reactions conventionally occur at the most active site. In addition, achieving precise control over site selectivity for remote C(sp 3 )-H activation presents an additional hurdle. Here we report an alternative modular method for alkene difunctionalization, encompassing radical-triggered translocation of functional groups and remote C(sp 3 )-H desaturation via photo/cobalt dual catalysis. By systematically combining radical addition, functional group migration and cobalt-promoted hydrogen atom transfer, we successfully effectuate the translocation of the carbon-carbon double bond and another functional group with precise site selectivity and remarkable E/Z selectivity. This redox-neutral approach shows good compatibility with diverse fluoroalkyl and sulfonyl radical precursors, enabling the migration of benzoyloxy, acetoxy, formyl, cyano and heteroaryl groups. This protocol offers a resolution for the simultaneous transformation of manifold sites.
(© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)
Databáze: MEDLINE
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