1, 3‐O‐Transposition or Trisubstituted Z‐Enol Ester? A Comparative Study of Reactions of Ynones

Release time:2021-07-02

DOI number:10.1002/asia.201900315

Journal:Chemistry–An Asian Journal

Abstract:Ynones are useful substrates for transition‐metal‐mediated synthesis. The AuI‐catalyzed 1,3‐O‐transposition is an important reaction of ynones. Recently, an efficient CuI‐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 AuI‐catalyst and CuI‐catalyst were further compared to interpret the essential cause of why the AuI‐catalyst prefers the 1,3‐O‐transpostion reaction. These conclusions might be helpful for the rational design of reactions of ynones.

Co-author:Changyuan Zhang, Penggang Yin

First Author:Tian‐Yu Sun

Correspondence Author:Kai Chen*, Tingting You*

Discipline:Natural Science

First-Level Discipline:Chemistry

Document Type:J

Volume:14

Issue:11

Page Number:1941-1944

Translation or Not:no

Date of Publication:2019-06-03

Included Journals:SCI

Links to published journals:https://onlinelibrary.wiley.com/doi/abs/10.1002/asia.201900315