Cleavage and Reassembly C≡C Bonds of Ynones to Access Highly Functionalized Ketones

Jiaxin Rong,^aHaowen Li,^aRui Fu,^aWangbin Sun,^aTeck-Peng Loh^ab* and Yaojia Jiang^a*

^aInstitute of Advanced Synthesis, School of Chemistry and Molecular Engineering,Nanjing Tech University, Nanjing 211816,China

^bDivision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637616 (Singapore)

Abstract:An expedient strategy has been designed to formally cleave C-C triple bond of ynones through copper-catalyzed carbene chemistry. It proceeds under mild reaction conditions in a highly step-economy process by simultaneously cleaving C≡C bonds as well as construct new C−C single 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 to involve an active cyclopropane intermediate and consequently takes placeviaa cascade ring-opening reaction. The method works for a spectrum of ynones andN-tosylhydrazones in good to excellent yields using a cheap copper catalytic system.

ACS Catal.DOI: 10.1021/acscatal.0c00381(最新影响因子：12.221)

文章链接：https://pubs.acs.org/doi/10.1021/acscatal.0c00381