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Gold-catalyzed [5,5]-rearrangement
journal contribution
posted on 2023-05-21, 07:38 authored by Hu, C, Farshadfar, K, Dietl, MC, Cervantes-Reyes, A, Wang, T, Adak, T, Rudolph, M, Rominger, F, Li, J, Alireza AriafardAlireza Ariafard, Hashmi, ASKA 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.
Funding
Australian Research Council
University of Wollongong
History
Publication title
ACS CatalysisVolume
11Issue
11Pagination
6510-6518ISSN
2155-5435Department/School
College Office - College of Sciences and EngineeringPublisher
American Chemical SocietyPlace of publication
United StatesRights statement
© 2021 American Chemical SocietyRepository Status
- Restricted