cs0c00381_si_001.pdf (8 MB)
Cleavage and Reassembly CC Bonds of Ynones to Access Highly Functionalized Ketones
journal contribution
posted on 2020-03-04, 20:15 authored by Jiaxin Rong, Haowen Li, Rui Fu, Wangbin Sun, Teck-Peng Loh, Yaojia JiangAn
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.