Gold-Catalyzed Asymmetric Thioallylation of Propiolates via Charge-Induced Thio-Claisen Rearrangement
- Authors
- Kim, Hanbyul; Jang, Jiwon; Shin, Seunghoon
- Issue Date
- Dec-2020
- Publisher
- AMER CHEMICAL SOC
- Citation
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.142, no.49, pp.20788 - 20795
- Indexed
- SCIE
SCOPUS
- Journal Title
- JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
- Volume
- 142
- Number
- 49
- Start Page
- 20788
- End Page
- 20795
- URI
- https://scholarworks.bwise.kr/hanyang/handle/2021.sw.hanyang/144258
- DOI
- 10.1021/jacs.0c09783
- ISSN
- 0002-7863
- 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.
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