Cleavage and reassembly C≡C bonds of ynones to access highly functionalized ketones

• Main Authors: Rong, Jiaxin, Li, Haowen, Fu, Rui, Sun, Wangbin, Loh, Teck-Peng, Jiang, Yaojia
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2022
• Subjects: Science::Biological sciences::Biochemistry; Ynones; Carbenes
• Online Access: https://hdl.handle.net/10356/155163
• Institution: Nanyang Technological University

An economical strategy has been designed to formally cleave CC bonds of ynones through copper-catalyzed carbene chemistry. It proceeds under mild reaction conditions in a step-economy process by simultaneously cleaving the CC bonds and constructing C-C bonds. Depending on the substitution of the ynones, the reactions can proceed efficiently to generate synthetically useful 1,4-ketoaldehydes and cyclopentenone compounds. A plausible pathway is proposed that involves an active cyclopropane intermediate that consequently undergoes a cascade ring-opening reaction. The method works for a spectrum of ynones and N-tosylhydrazones that give good to excellent yields using a cheap copper catalytic system.