Synthesis 2021; 53(24): 4644-4653
DOI: 10.1055/a-1559-3020
paper

Synthesis of γ,δ-Unsaturated Esters and Amides via Au(I)-Catalyzed Reactions of Aryl Ynol Ethers or Ynamides with Allylic Alcohols

Souta Misawa
a   Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
,
Asaki Miyairi
a   Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
,
a   Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
,
b   Department of Chemistry and Centre for Sustainable Chemistry, Ghent University, Krijgslaan 281, S-3, 9000 Ghent, Belgium
,
a   Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japan
› Author Affiliations
This work was financially supported in part by Grants-in Aid for Scientific Research (B) (No. 20H0360) and Scientific Research (C) (No. 20K06960) from the Japan Society of the Promotion of Science (JSPS). The Nagase Science Technology Foundation (for Y.S.) and the Akiyama Life Science Foundation (for Y.O.) are also acknowledged for financial support. S.P.N. thanks the Bijzonder Onderzoeksfonds UGent (UGent BOF) for starting and advanced grants.


Abstract

Polarized alkynes such as ynol ethers and ynamides have attracted much attention due to their inherent unique reactivity. Herein, we report Au(I)-catalyzed hydroalkoxylation/Claisen rearrangement cascade reactions of aryl ynol ethers and ynamides with allylic alcohols. At the first stage (hydroalkoxylation) of this cascade reaction, attack of allylic alcohols to aryl ynol ethers or ynamides occurs at the α-position of the polarized alkynes in a completely regioselective manner. Claisen rearrangement of the resulting adducts subsequently takes place to give γ,δ-unsaturated esters or amides, respectively. The [Au(IPr)NTf2] catalyst is most effective for this reaction, and the reaction proceeds under mild conditions (in the case of aryl ynol ether: in THF, 60 °C; in the case of ynamides: in toluene, 80 °C) in an atom-economical way.

Supporting Information



Publication History

Received: 28 June 2021

Accepted after revision: 27 July 2021

Publication Date:
27 July 2021 (online)

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
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