92633-43-7

Upstream product

• 286-20-4 cyclohexane-1,2-epoxide 
• 14032-04-3 (1R*,2R*)-2-thiophenylcyclohexanol 
• 108-98-5 thiophenol 
• 110-83-8 cyclohexene 
• 591-50-4 iodobenzene 
• 66003-76-7 Diphenyliodonium triflate 
• 824-79-3 sodium 4-methylbenzenesulfinate 
• 98-80-6 phenylboronic acid 
• 2973-86-6 lithium thiophenoxide 
• 286-20-4 cyclohexene oxide 
• 873-55-2 sodium benzenesulfonate 

Downstream Products

• 110452-14-7 2-phenylthiocyclohexanone 
• 73843-10-4 2-(phenylsulphonyl)cyclohexanone 

Relevant academic research and scientific papers

Silyloxymethanesulfinate as a sulfoxylate equivalent for the modular synthesis of sulfones and sulfonyl derivatives

An efficient protocol for the modular synthesis of sulfones and sulfonyl derivatives has been developed utilizing sodium tert-butyldimethylsilyloxymethanesulfinate (TBSOMS-Na) as a sulfoxylate (SO22-) equivalent. TBSOMS-Na, easily prepared from the commercial reagents Rongalite and TBSCl, serves as a potent nucleophile in S-alkylation and Cu-catalyzed S-arylation reactions with alkyl and aryl electrophiles. The sulfone products thus obtained can undergo the second bond formation at the sulfur center with various electrophiles without a separate unmasking step to afford sulfones and sulfonyl derivatives such as sulfonamides and sulfonyl fluorides.

Copper(i)-catalyzed sulfonylative Suzuki-Miyaura cross-coupling

Using a simple copper(i) catalyst has allowed a high yielding sulfonylative-Suzuki-Miyaura cross-coupling reaction to be developed. The process provides a single step route to diaryl sulfones from the direct combination of aryl boronic acids, sulfur dioxide and aryl iodides, and represents the first sulfonylative variant of a classic cross-coupling reaction. Sulfur dioxide is delivered from the surrogate reagent, DABSO. Variation of the reaction conditions allowed interruption of the sulfonylative-Suzuki coupling, resulting in the formation of a presumed Cu-sulfinate intermediate. These sulfinates could be trapped as their sodium salts and treated with electrophiles to allow access to arylalkyl sulfones, β-hydroxyl sulfones, sulfonamides and sulfonyl fluorides.

Catalyst-free oxidation of sulfides to sulfoxides and diethylamine catalyzed oxidation of sulfides to sulfones using Oxone as an oxidant

Abstract: We describe here our journey from the failure of our attempts in controlled oxidation of sulfides to sulfoxides using an Oxone–KBr combination to our success in the development of a catalyst-free protocol for the oxidation of sulfides to sulfoxides using Oxone as an oxidant. We also describe the failure of our attempts at the oxidation of sulfides to sulfones using an excess of Oxone–KBr as well as Oxone, and our success towards the development of a rapid, scalable and chromatography-free protocol for the oxidation of sulfides to sulfones using diethylamine–Oxone as an unprecedented catalyst–oxidant combination.

An approach toward the synthesis of β-hydroxy sulfones on water

Various β-hydroxyl sulfones are prepared by regioselective ring opening of epoxides with sodium salt of sulfinate on water. This is an efficient protocol which avoids hazardous and moisture sensitive catalysts.

A general and efficient method for the selective synthesis of β-hydroxy sulfides and β-hydroxy sulfoxides catalyzed by gallium(III) triflate

(Chemical Equation Presented) Gallium(III) triflate-catalyzed ring opening of epoxides affords β-hydroxy sulfides with high regioselectivity and chemoselectivity in high yields (84-97%) under solvent-free conditions. Additionally, a simple, efficient, and environmentally benign one-pot procedure for the synthesis of β-hydroxy sulfoxides in sole water has been developed for the first time. The process, promoted by a H2O 2-Ga(OTf)3 system, affords β-hydroxy sulfoxides in high yields (81-94%) and high chemoselectivity without any detectable overoxidation to β-hydroxy sulfones. The catalyst could be recovered easily after the reactions and reused without evident loss of activity.

Phenylsulfonyl as a β participating group

The phenylsulfonyl group (PhSQ2) has been examined for its β effect properties. The stereochemical relationship was varied between phenylsulfonyl and a nucleophilic leaving group (nucleofuge) separated by two carbons. Mechanisms were distinguished through solvent effects on rates and products. When the stereochemistry between the two groups was gauche, the only effect of phenylsulfonyl was strong inductive retardation in a mechanism involving solvent participation. With the antiperiplanar stereochemistry, however, the mechanism clearly changed to carbocation formation with a small kinetic acceleration. Thus, phenylsulfonyl is a weak β effect substituent. This remarkable property for a strongly electron-withdrawing group occurs most likely through hyperconjugation or possibly through anchimeric assistance.

Stereoselective Synthesis of a Bicyclic Ketooxetane via a Thionium Ion-Mediated Cyclisation Reaction

The synthesis of a bicyelic ketooxetane using as the key step the ethylaluminium dichloride-mediated cyclisation of a Z-silyl enol ether onto a thionium ion 'trigger' attached to a five-membered carbocyclic template is described. Attempted cyclisation of the analogous substrate possessing a six-membered ring did not afford the oxetane, but instead the product of 1,2-hydride shift. The mechanism of this unexpected transformation was conclusively established by analysis of the products of attempted cyclisation of a deuterium-labelled substrate.