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Gold-catalyzed [5,5]-rearrangement

Citation

Hu, C and Farshadfar, K and Dietl, MC and Cervantes-Reyes, A and Wang, T and Adak, T and Rudolph, M and Rominger, F and Li, J and Ariafard, A and Hashmi, ASK, Gold-catalyzed [5,5]-rearrangement, ACS Catalysis, 11, (11) pp. 6510-6518. ISSN 2155-5435 (2021) [Refereed Article]

Copyright Statement

2021 American Chemical Society

DOI: doi:10.1021/acscatal.1c01108

Abstract

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 Details

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:3
Deposited By:College Office - CoSE
Deposited On:2022-05-16
Last Modified:2022-07-19
Downloads:0

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