Synthesis 2014; 46(16): 2149-2154
DOI: 10.1055/s-0034-1378281
special topic
© Georg Thieme Verlag Stuttgart · New York

THF Solvent as a Proton Shuttle in the AuCl3-Catalyzed Cycloisomerization of a Bromoallenyl Ketone: A Mechanistic DFT Study

Wei Guo
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, P. R. of China   Email: xyz@wzu.edu.cn
,
Yuanzhi Xia*
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, P. R. of China   Email: xyz@wzu.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 28 April 2014

Accepted after revision: 16 May 2014

Publication Date:
24 June 2014 (eFirst)

Abstract

The solvent effect on the regiochemistry of the AuCl3-catalyzed cycloisomerization of a bromoallenyl ketone was evaluated by DFT calculations, which provided theoretical rationale for the original experimental findings from the Gevorgyan group. Upon the generation of the gold carbenoid intermediate from cyclization of the allene precursor, the tetrahydrofuran solvent could act as a proton shuttle to assist the 1,2-H migration to afford the 2-bromofuran product. This solvent-involved pathway is lower in energy than the 1,2-Br migration and thus leads to a solvent-controlled switch of regioselectivity in the reaction concerned.

Supporting Information

 
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