1, 3‐O‐Transposition or Trisubstituted Z‐Enol Ester? A Comparative Study of Reactions of Ynones. Issue 11 (8th May 2019)

• Record Type: Journal Article
• Authors: Sun, Tian‐Yu; Chen, Kai; Zhang, Changyuan; You, Tingting; Yin, Penggang
• Is Part Of: Chemistry, an Asian journal. Volume 14:Issue 11(2019)
• Page Start: 1941
• Page End: 1944
• Publication Date: 2019-05-08
• Subjects: 1, 3-O-transposition -- density functional theory -- reaction mechanisms -- trisubstituted Z-enol esters -- ynones; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201900315
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: Ynones are useful substrates for transition‐metal‐mediated synthesis. The Au I ‐catalyzed 1, 3‐O‐transposition is an important reaction of ynones. Recently, an efficient Cu I ‐catalyzed synthesis of trisubstituted Z ‐enol esters via interrupting the traditional 1, 3‐O‐transposition reaction of ynones was reported by Zhu's group. Herein, density functional theory studies disclosed that the hydrogen bond formed by carboxylic acid plays an important role for the reactivity and selectivity in this novel reaction. A qualitative rule was also found to explain the substituent effect in the ynone substrate, and this is consistent with experiments. The Au I ‐catalyst and Cu I ‐catalyst were further compared to interpret the essential cause of why the Au I ‐catalyst prefers the 1, 3‐O‐transpostion reaction. These conclusions might be helpful for the rational design of reactions of ynones. Abstract : Interrupting 1, 3‐O‐transposition of ynones : The reaction mechanism of the Cu I ‐catalyzed synthesis of trisubstituted Z‐enol esters via interrupting the traditional 1, 3‐O‐transposition reaction of ynone is disclosed. The hydrogen bond formed by carboxylic acid plays an important role for the reactivity and selectivity. A qualitative rule explains the substituent effect in ynone substrates. The electronic effect explains why Au I ‐catalyst prefers 1, 3‐O‐transposition.