Gold-Catalyzed Asymmetric Thioallylation of Propiolates via Charge-Induced Thio-Claisen Rearrangement
- Title
- Gold-Catalyzed Asymmetric Thioallylation of Propiolates via Charge-Induced Thio-Claisen Rearrangement
- Author
- 신승훈
- Issue Date
- 2020-11
- Publisher
- AMER CHEMICAL SOC
- Citation
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v. 142, no. 49, page. 20788-20795
- Abstract
- A gold(I)-catalyzed enantioselective thioallylation of propiolates with ally! sulfides is described. The key mechanistic element is a sulfonium-induced Claisen rearrangement which helps minimize the allyl dissociation and render higher enantioselectivity. This protocol features remarkable scope of the allyl moiety, allowing enantiocontrolled synthesis of all-carbon quaternary centers, and exhibits exceptional functional group compatibility with many Lewis bases and ir-bonds. This intermolecular variant of Claisen rearrangement forges both C-S and C-C bonds concomitantly, providing efficient access to interesting optically active organosulfur compounds which can be transformed further through the vinyl sulfide as a functional handle. The rate of the reaction was zeroth order with respect to allyl sulfides, which suggested a reversible inhibition, providing a resting state for the catalyst. The Hammett plot displayed a correlation with sigma(p) values, suggesting a turnover-limiting sigmatropic rearrangement where decreased electron-density on sulfur accelerated the rearrangement.
- URI
- https://pubs.acs.org/doi/10.1021/jacs.0c09783https://repository.hanyang.ac.kr/handle/20.500.11754/172611
- ISSN
- 0002-7863; 1520-5126
- DOI
- 10.1021/jacs.0c09783
- Appears in Collections:
- COLLEGE OF NATURAL SCIENCES[S](자연과학대학) > CHEMISTRY(화학과) > Articles
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