Visible light-mediated NHCs and photoredox co-catalyzed radical 1,2-dicarbonylation of alkenes for 1,4-diketones

• Published in: Science China. Chemistry Vol. 65; no. 10; pp. 1938 - 1944
• Main Authors: Wang, Lihong, Sun, Jiaqiong, Xia, Jiuli, Li, Mingrui, Zhang, Lianjin, Ma, Ruiyang, Zheng, Guangfan, Zhang, Qian
• Format: Journal Article
• Language: English
• Published: Beijing Science China Press 01.10.2022; Science Press; Springer Nature B.V
• Subjects: Acids; Alkenes; Carbonyl compounds; Carbonyl groups; Carbonyls; Chemistry; Chemistry and Materials Science; Chemistry, Multidisciplinary; Chemistry/Food Science; Chromatography; Cooperation; Cross coupling; Diketones; Fluorides; Photocatalysis; Physical Sciences; Science & Technology; Solvents; Substrates; 1, 4-diketones; radical 1, 2-dicarbonylation; photocatalysis; alkenes; NHCs; 1; STYRENES; radical 1; 2-dicarbonylation; ACYLATION; 4-diketones; ENONES; METAL; DIACYLATION
• ISSN: 1674-7291; 1869-1870
• DOI: 10.1007/s11426-022-1328-5

Alkenes are ubiquitous, and the difunctionalization of alkenes represents one of the most practical approaches for the construction of value-added compounds. Dicarbonylation of alkenes provides direct access to value-added 1,4-dicarbonyl compounds. However, selectivity control for unsymmetric 1,2-dicarbonylation is of great challenge. We herein describe NHCs and photocatalysis co-catalyzed three-component radical 1,2-dicarbonylation of alkenes by distinguishing two carbonyl groups, providing structurally diversified 1,4-diketones. Distinct properties of acyl radical and NHCs-stabilized ketyl radical contributed to selectivity control. Acyl radicals are rapidly added to alkenes delivering alkyl radicals, which undergo subsequent radical-radical cross-coupling with NHCs-stabilized ketyl-type radicals, affording 1,2-dicarbonylation products. This transformation features mild reaction conditions, broad substrate scope, and excellent selectivity, providing a general and practical approach for the dicarbonylation of olefins.