Copper-catalyzed aerobic nitrogen-migration cyanation and oxygenation of unsaturated ketoximes via the C=C bond cleavage: facile access to 4-oxobutanenitriles

作者：Liu, Xiao-Dong; Li, Yang; Hu, Ming^*; Wang, Qiu-An^*; Li, Jin-Heng^*

来源：Organic Chemistry Frontiers, 2022, 9(24): 6920-6925.

DOI：10.1039/d2qo01553f

• UNACTIVATED ALKENES
• CYCLIC NITRONES
• OXIMES
• ISOXAZOLINES
• DIOXYGENATION
• OXYAMINATION
• CYCLIZATION
• ANTAGONISTS
• GENERATION

A new copper-catalyzed aerobic synthesis of 4-oxobutanenitriles by the nitrogen-migration cyanation and oxygenation of gamma,delta-unsaturated ketoximes at room temperature is developed. By means of a copper(0) powder catalyst, the nitrogen-migration cyanation and oxygenation of unsaturated ketoximes with O(2 )via a radical intramolecular 5-exo-trig cyclization, C=C double bond cleavage and ring-opening process efficiently execute to assemble 4-oxobutanenitriles. Mechanistic studies indicate that these processes include radicals initiating the reaction from the oxime side and the superoxide radical formation.

• 单位
  南昌航空大学; 兰州大学