Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (1): 284-296.DOI: 10.6023/cjoc202008044 Previous Articles     Next Articles


钌催化末端炔丙醇经亚丙二烯基卡宾中间体氧化产生亚甲基烯酮: α, β-不饱和羧酸衍生物的合成

王新宇a, 李其欢a, 温庭斌a,*()   

  1. a 厦门大学化学化工学院化学系 福建厦门 361005
  • 收稿日期:2020-08-24 修回日期:2020-09-07 发布日期:2020-09-09
  • 通讯作者: 温庭斌
  • 作者简介:
    * Corresponding author. E-mail:
  • 基金资助:

Ruthenium-Catalyzed Oxygenative Transformation of Terminal Propargyl Alcohols to Metheyleneketenes via Allenylidene Intermedia-tes: Synthesis ofα,β-Unsaturated Carboxylic Acid Derivatives

Xinyu Wanga, Qihuan Lia, Tingbin Wena,*()   

  1. a Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005
  • Received:2020-08-24 Revised:2020-09-07 Published:2020-09-09
  • Contact: Tingbin Wen
  • Supported by:
    the National Natural Science Foundation of China(21971215)

A ruthenium-catalyzed oxygenative transformation of terminal propargyl alcohols to metheyleneketenes via allenylidene intermediates has been developed for the synthesis of a variety of α, β-unsaturated carboxylic acid derivatives. Mechanistic study experiments disclosed that oxygen transfer from pyridine- N-oxide to ruthenium allenylidene generated from the reaction of catalyst CpRuCl(PPh3)2/NaBPh4 with terminal propargyl alcohol resulted in the formation of reactive methyleneketene intermediate, which was trapped into nucleophilic addition reactions to afford α, β-unsaturated product. This reaction offers an attractive complementary strategy to the traditional approach for the synthesis of this class of unsaturated compounds, but in a distinct mechanism, which provides a novel method for the transformation of propargylic alcohols. The metal allenylidene-to-methyleneketene transformation also represents a new mechanistic modality for metal allenylidene-mediated catalysis.

Key words: Keywords ruthenium, allenylidene, propargyl alcohol, oxygen-transfer, methyleneketene, ketene