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Updated: Aug 10, 2025

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts
Published on: February 24, 2015
Regio- and stereospecific cis-hydrophenoxylation of ynamides with acidic phenols
Ting Wang1, Yuyan Wan1, Mingyao Xu1
1Guangzhou Municipal and Guangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, the NMPA and State Key Laboratory of Respiratory Disease, School of Pharmaceutical Sciences and the Fifth Affiliated Hospital, Guangzhou Medical University, Guangzhou, Guangdong 511436, P. R. China. zzeng@gzhmu.edu.cn.
Abstract:
Herein we describe a self-acid-enabled chemo-, regio-, and stereospecific cis-hydrophenoxylation of ynamides under reagent-free conditions. The presence of a non-polar solvent such as toluene was found to be beneficial to facilitate the rate-limiting proton transfer between phenols and ynamides to form an intimate ion pair, which is followed by a swift nucleophilic attack of the phenolate oxygen on keteniminium, fulfilling the overall hydrofunctionalization event. This protocol is operationally simple and easily scalable, tolerates a wide variety of functional groups, and shows good compatibility with the requirements of modern green chemistry.
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