52322-54-0Relevant academic research and scientific papers
Catalytic enantioselective oxysulfenylation ofo-vinylanilides
Anbarasan, Pazhamalai,Kesavan, Arunachalam
supporting information, p. 282 - 285 (2022/01/06)
Tf2NH-assisted BINAM-derived thiophosphoramide catalysis has been accomplished for the enantioselective oxysulfenylation ofo-vinylanilides withN-(aryl/alkylthio)imides. The developed reaction offers access to diverse substituted aryl/alkylthio
N-thioaryl/alkyl o-sulfonylbenzoylimine and preparation method and application thereof
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Paragraph 0019; 0034; 0036-0041, (2019/10/10)
The invention relates to N-thioaryl/alkyl o-sulfonylbenzoylimine and a preparation method and application thereof. O-sulfonylbenzoylimine is taken as a raw material and reacts with sodium hydride to obtain sodium salt of the o-sulfonylbenzoylimine; the prepared sodium salt of the o-sulfonylbenzoylimine reacts with benzenesulfenyl chloride or alkyl sulfenyl chloride to obtain the N-thioaryl/alkyl o-sulfonylbenzoylimine which can be applied to a thioarylation/alkylation reaction. Compared with the prior art, the preparation method involved in the invention has the advantages that reaction conditions are mild, the chemical yield is high, a new thioaryl/alkyl reagent which is not sensitive to water and air and is relatively high in stability is synthesized, the prepared N-thioaryl/alkyl o-sulfonylbenzoylimine can be used as an electrophilic thioarylation/alkylation reagent with relatively high activity, and a very good application prospect is realized.
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
supporting information, p. 15411 - 15418 (2019/11/14)
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.
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.
