A highly efficient gold-catalyzed cycloisomerization of 1,5-diynes was developed. Various functional groups are tolerated under the mild reaction conditions, which provides an alternative approach for the synthesis of indeno[1,2-c]furans. On the basis of mechanistic studies, including crossover experiments, deuterium labeling, and computational chemistry, the product formation proceeds via a formal [5,5]-sigmatropic rearrangement, a yet unknown reactivity pattern in gold catalysis. Instead of a synchronous concerted [5,5]-sigmatropic rearrangement and beyond an asynchronous concerted mode, each involving a single transition state, two energetically low transition states (1.8 and 5.6 kJ/mol) and an intermediate associate of the migrating benzyl cation and the vinyl gold species could be located in the computations.

Item Type:	Refereed Article
Keywords:	gold catalysis, reaction mechanism, DFT calculations, rearrangement
Research Division:	Chemical Sciences
Research Group:	Physical chemistry
Research Field:	Catalysis and mechanisms of reactions
Objective Division:	Expanding Knowledge
Objective Group:	Expanding knowledge
Objective Field:	Expanding knowledge in the chemical sciences
UTAS Author:	Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:	150046
Year Published:	2021
Funding Support:	Australian Research Council (DP180100904)
Web of Science® Times Cited:	10
Deposited By:	College Office - CoSE
Deposited On:	2022-05-16
Last Modified:	2022-08-23
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