160968-44-5Relevant academic research and scientific papers
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.
The Geometry of the Carbanionic Moiety Influences the Non-Induced Diastereoselectivity of the -Wittig Rearrangement of Lithiated Diallyl Ethers
Goeppel, Dirk,Muenster, Ingo,Brueckner, Reinhard
, p. 3687 - 3708 (2007/10/02)
Lithiated diallyl ethers with cis- or trans-configuration of the anionic moiety were generated from the diallyl ethers 10, from the vinylogous O,S-acetals 13, and from the O,S-acetals 14 by treatment with nBuLi (in the case of 10) or with lithium naphthal
