Synthesis, Table of Contents Synthesis 2014; 46(16): 2149-2154DOI: 10.1055/s-0034-1378281 special topic © Georg Thieme Verlag Stuttgart · New YorkTHF Solvent as a Proton Shuttle in the AuCl3-Catalyzed Cycloisomerization of a Bromoallenyl Ketone: A Mechanistic DFT Study Authors Author Affiliations 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 Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) 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. Key words Key wordscarbenoids - cyclization - heterocycles - homogeneous catalysis - regioselectivity - solvent effects Full Text References References For recent reviews, see: 1a Rudolph M, Hashmi AS. K. Chem. Soc. Rev. 2012; 41: 2448 1b Garayalde D, Nevado C. ACS Catal. 2012; 2: 1462 1c Corma A, Leyva-Pérez A, Sabater MJ. Chem. Rev. 2011; 111: 1657 1d Krause N, Winter C. Chem. Rev. 2011; 111: 1994 1e Yamamoto Y, Gridnev ID, Patil NT, Jin T. Chem. Commun. 2009; 5075 1f Abu Sohel SM, Liu R.-S. Chem. Soc. Rev. 2009; 38: 2269 1g Gorin DJ, Sherry BD, Toste FD. Chem. 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