Copper-catalyzed 1,2,2-trifunctionalization of maleimides with 1,7-enynes and oxime esters via radical relay/1,5-hydrogen-atom transfer

• Published in: ORGANIC CHEMISTRY FRONTIERS Vol. 10; no. 24; pp. 6096 - 6102
• Main Authors: Jiang, Li-Lin, Qiu, Hui, Zhou, Yu, Wang, Ling-Tao, Yang, Wen-Hui, Deng, Chao, Wei, Wen-Ting
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 05.12.2023; Royal Society of Chemistry
• Subjects: Alkenes; Chemistry; Chemistry, Organic; Copper; Covalent bonds; Density functional theory; Esters; Hydrogen atoms; Organic chemistry; Oxime esters; Physical Sciences; Radicals; Relay; Science & Technology; Substrates; FUNCTIONALIZATION; ATOM-TRANSFER; ALKENES; CASCADE; TRIFUNCTIONALIZATION; CYCLIZATION
• ISSN: 2052-4129; 2052-4110; 2052-4110
• DOI: 10.1039/d3qo01431b

The trifunctionalization of alkenes has emerged as a versatile strategy for the efficient construction of diverse structural units and complex molecules in synthetic chemistry. Herein, we describe a novel 1,2,2-trifunctionalization of maleimides with 1,7-enynes and oxime esters through simultaneous construction of four C-C bonds and a C=N bond in one pot based on the radical relay/1,5-hydrogen-atom transfer (HAT) processes under a mild copper catalytic system. The resulting reaction of spirocyclic derivatives displays high chemical selectivity, broad substrate scope, as well as high atom- and step-economy. Preliminary control experiments and density functional theory (DFT) calculations reveal sequential functionalizations and cyclizations in this transformation.