121585-24-8Relevant articles and documents
Catalytic, Enantioselective Sulfenylation of Ketone-Derived Enoxysilanes
Denmark, Scott E.,Rossi, Sergio,Webster, Matthew P.,Wang, Hao
supporting information, p. 13016 - 13028 (2015/09/15)
A catalytic, enantioselective, Lewis base-catalyzed α-sulfenylation of silyl enol ethers has been developed. To avoid acidic hydrolysis of the silyl enol ether substrates, a sulfenylating agent that did not require additional Br?nsted acid activation, namely N-phenylthiosaccharin, was developed. Three classes of Lewis bases - tertiary amines, sulfides, and selenophosphoramides - were identified as active catalysts for the α-sulfenylation reaction. Among a wide variety of chiral Lewis bases in all three classes, only chiral selenophosphoramides afforded α-phenylthio ketones in generally high yield and with good enantioselectivity. The selectivity of the reaction does not depend on the size of the silyl group but is highly sensitive to the double bond geometry and the bulk of the substituents on the double bond. The most selective substrates are those containing a geminal bulky substituent on the enoxysilane. Computational analysis revealed that the enantioselectivity arises from an intriguing interplay among sterically guided approach, distortion energy, and orbital interactions.
Asymmetric Sulfenylation of Tin(II) Enolates of Ketones and 3-Acyl-2-oxazolidones. Application to the Synthesis of Optically Active Epoxides
Yura, Takeshi,Iwasawa, Nobuharu,Clark, Richard,Mukaiyama, Teruaki
, p. 1809 - 1812 (2007/10/02)
In the presence of chiral diamines, the reaction between tin(II) enolates of ketones or 3-acyl-2-oxazolidones and thiosulfonates proceeds smoothly to give the corresponding β-keto sulfides with high enetioselectivity.Further, optically active epoxides are prepared from these β-keto sulfides.
