40964-63-4Relevant articles and documents
Lewis Base/Br?nsted Acid Co-Catalyzed Asymmetric Thiolation of Alkenes with Acid-Controlled Divergent Regioselectivity
Luo, Hui-Yun,Dong, Jia-Wei,Xie, Yu-Yang,Song, Xu-Feng,Zhu, Deng,Ding, Tongmei,Liu, Yuanyuan,Chen, Zhi-Min
, p. 15411 - 15418 (2019)
A divergent strategy for the facile preparation of various enantioenriched phenylthio-substituted lactones was developed based on Lewis base/Br?nsted acid co-catalyzed thiolation of homoallylic acids. The acid-controlled regiodivergent cyclization (6-endo vs. 5-exo) and acid-mediated stereoselective rearrangement of phenylthio-substituted lactones were explored. Experimental and computational studies were performed to clarify the origins of the regioselectivity and enantioselectivity. The calculation results suggest that C?O and C?S bond formation might occur simultaneously, without formation of a commonly supposed catalyst-coordinated thiiranium ion intermediate and the potential π–π stacking between substrate and SPh as an important factor in the enantio-determining step. Finally, this methodology was applied in the rapid syntheses of the bioactive natural products (+)-ricciocarpin A and (R)-dodecan-4-olide.
Flexible Construction of Functionalized-Pyrroles under Palladium or Copper Catalysis in the Presence of BF3 ? Et2O
Liu, Yin,Liu, Teng,Yan, Biwei,Wei, Kun,Guo, Wusheng
, p. 916 - 921 (2022/01/26)
We have developed a flexible approach enabling the access to highly functionalized pyrroles under palladium or copper catalysis in the presence of BF3 ? Et2O. This catalytic methodology utilizes commercially available amines as react
Gold-Catalyzed Asymmetric Thioallylation of Propiolates via Charge-Induced Thio-Claisen Rearrangement
Kim, Hanbyul,Jang, Jiwon,Shin, Seunghoon
supporting information, p. 20788 - 20795 (2020/11/27)
A gold(I)-catalyzed enantioselective thioallylation of propiolates with allyl 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 π-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 σp values, suggesting a turnover-limiting sigmatropic rearrangement where decreased electron-density on sulfur accelerated the rearrangement.
