title: Unprecedented reactions: from epichlorohydrin to epoxyglycidyl substituted divinyl ether and its conversion into epoxyglycidyl propargyl ether.
abstract: The reaction of epichlorohydrin with concentrated sodium hydroxide in hexane under phase transfer conditions has surprisingly led to the formation of the symmetrical di(3-epoxyglycidyl-1-propenyl) ether 1 which contains both nucleophilic and electrophilic moieties. When it was reacted with n-butyllithium, intermediate 1 once again surprisingly generated epoxyglycidyl propargyl ether, which was further reacted in situ with a variety of benzaldehydes to furnish the corresponding substituted propargylic alcohols in good yields. While the reaction is operationally simple, it provides a powerful method for the synthesis of the important products from commodity materials such as epichlorohydrin. Moreover, these reactions may have revealed that some fundamental properties of the hydroxide anion in those once thought straightforward reactions are not well understood. A careful analysis of the experimental data suggests that an unprecedented concerted elimination of the epoxyglycidyl ether with sodium hydroxide may be operative and an alpha deprotonation followed by alpha elimination of the di(3-epoxyglycidyl-1-propenyl) ether with alkyllithium may have been involved.
authors.affiliation: Laboratory of Medicinal Chemistry, Guangzhou Institute of Biomedicine and Health, The Chinese Academy of Sciences, Guangzhou 510530, China.
authors.forename: Yiwu
authors.initials: Y
authors.lastname: Yao
authors.affiliation: The Methodist Hospital Research Institute, Houston, Texas 77030, United States.
authors.forename: Zheng
authors.initials: Z
authors.lastname: Li
authors.affiliation: Laboratory of Medicinal Chemistry, Guangzhou Institute of Biomedicine and Health, The Chinese Academy of Sciences, Guangzhou 510530, China.
authors.forename: Yatao
authors.initials: Y
authors.lastname: Qiu
authors.affiliation: Laboratory of Medicinal Chemistry, Guangzhou Institute of Biomedicine and Health, The Chinese Academy of Sciences, Guangzhou 510530, China.
authors.forename: Jinhong
authors.initials: J
authors.lastname: Bai
authors.affiliation: Laboratory of Medicinal Chemistry, Guangzhou Institute of Biomedicine and Health, The Chinese Academy of Sciences, Guangzhou 510530, China.|State Key Laboratory of Natural Medicines and Center of Drug Discovery, China Pharmaceutical University, Nanjing 210009, China.
authors.forename: Jinyue
authors.initials: J
authors.lastname: Su
authors.affiliation: State Key Laboratory of Natural Medicines and Center of Drug Discovery, China Pharmaceutical University, Nanjing 210009, China.
authors.forename: Dayong
authors.initials: D
authors.lastname: Zhang
authors.affiliation: Laboratory of Medicinal Chemistry, Guangzhou Institute of Biomedicine and Health, The Chinese Academy of Sciences, Guangzhou 510530, China.
authors.forename: Sheng
authors.initials: S
authors.lastname: Jiang