71899-81-5

Upstream product

• 100-52-7 benzaldehyde 
• 3185-99-7 Methyl p-tolyl sulfone 
• 96-09-3 styrene oxide 
• 824-79-3 sodium 4-methylbenzenesulfinate 
• 100-42-5 styrene 
• 98-59-9 p-toluenesulfonyl chloride 
• 657-84-1 sodium tosylate 
• 1576-35-8 toluene-4-sulfonic acid hydrazide 
• 106-45-6 para-thiocresol 
• 42330-51-8 rac-(R)-1-phenyl-2-(p-tolylthio)ethan-1-ol 
• 31378-03-7 1-phenyl-2-tosylethanone 
• 105769-48-0 1-((2-chloro-2-phenylethyl)sulfonyl)-4-methylbenzene 
• 96938-08-8 (R)-(+)-2-hydroxy-2-phenylethyl p-tolyl sulfide 
• 17199-29-0 (S)-Mandelic acid 

Downstream Products

• 16212-08-1 1-methyl-4-((2-phenylallyl)sulfonyl)benzene 
• 16212-08-1 1-methyl-4-[(E)-2-phenylethenesulfonyl]benzene 
• 105769-48-0 (R)-(+)-2-chloro-2-phenylethyl p-tolyl sulfone 

Relevant academic research and scientific papers

Dioxygen-Triggered Oxosulfonylation/Sulfonylation of Terminal Olefins toward β-Keto Sulfones/Sulfones

A dioxygen-triggered oxosulfonylation/sulfonylation of unactivated olefins to achieve β-keto sulfones/sulfones has been developed. Interestingly, pluralistic mechanisms were found when different types of compounds were applied as substrates, and different products were achieved. The reaction is carried out with a high atomic efficiency in the absence of a metal and a catalyst at room temperature under an air atmosphere. Importantly, as a proof-of-concept, a bioactive molecule was synthesized on a gram-scale level using this method.

Copper-Catalyzed Aerobic Oxidative Cleavage of Unstrained Carbon-Carbon Bonds of 1,1-Disubstituted Alkenes with Sulfonyl Hydrazides

Alkoxy radical-mediated carbon-carbon bond cleavages have emerged as a powerful strategy to complement traditional ionic-type transformations. However, carbon-carbon cleavage reaction triggered by alkoxy radical intermediate derived from the combination of alkyl radical and dioxygen, is scarce and underdeveloped. Herein, we report alkoxy radical, which was generated from alkyl radical and dioxygen, mediated selective cleavage of unstrained carbon-carbon bond for the oxysulfonylation of 1,1-disubstituted alkenes, providing facile access to a variety of valuable β-keto sulfones. Mechanistic experiments indicated alkoxy radical intermediate that underwent subsequent regioselective β-scission might be involved in the reaction and preliminary computational studies were conducted to provide a detailed explanation on the regioselectivity of the C—C bond cleavage. Notably, the strategy was successfully applied for constructing uneasily obtained architecturally intriguing molecules.

Chemoenzymatic Oxosulfonylation-Bioreduction Sequence for the Stereoselective Synthesis of β-Hydroxy Sulfones

A series of optically active β-hydroxy sulfones has been obtained through an oxosulfonylation-stereoselective reduction sequence in aqueous medium. Firstly, β-keto sulfones were synthesized from arylacetylenes and sodium sulfinates to subsequently develop the carbonyl reduction in a highly selective fashion using alcohol dehydrogenases as biocatalysts. Optimization of the chemical oxosulfonylation reaction was investigated, finding inexpensive iron(III) chloride hexahydrate (FeCl3 ? 6H2O) as the catalyst of choice. The selection of isopropanol in the alcohol-water media resulted in high compatibility with the enzymatic process for enzyme cofactor recycling purposes, providing a straightforward access to both (R)- and (S)-β-hydroxy sulfones. The practical usefulness of this transformation was illustrated by describing the synthesis of a chiral intermediate of Apremilast. Interestingly, the development of a chemoenzymatic cascade approach avoided the isolation of β-keto sulfone intermediates, which allowed the preparation of chiral β-hydroxy sulfones in high conversion values (83–94 %) and excellent optical purities (94 to >99 % ee).

Copper-Catalyzed Chloro-Arylsulfonylation of Styrene Derivatives via the Insertion of Sulfur Dioxide

A copper-catalyzed four-component chloro-arylsulfonylation of styrene derivatives with aryldiazonium tetrafluoroborates, lithium chloride, and ex-situ generated sulfur dioxide (from SOgen) is presented. This sulfonylation features good functional group compatibility, mild reaction conditions, excellent regioselectivity, and good yields. The robustness and potential of this method have also been successfully demonstrated by a gram-scale reaction. Based on experimental study, a radical-involved mechanism is proposed for the transformation.

Ag-catalyzed sulfonylation-peroxidation of alkenes with sulfonyl hydrazides and T-hydro

The sulfonylation-peroxidation of alkenes with sulfonyl hydrazides and T-hydro was developed. The Ag-catalyzed three-component peroxidation provides a method for synthesis of a variety of β-sulfonyl peroxides, which could be converted into various sulfone derivatives.

PQS-enabled visible-light iridium photoredox catalysis in water at room temperature

An amphoteric PQS-attached photocatalyst has been prepared that undergoes self-aggregation in water into nanomicelles. This covalently bound species enables Ir-based photoredox catalysis to be conducted in the absence of additives or co-solvents. Representative reactions are described using this new catalytic system, which require no additional investment of external energy in the form of heating or cooling. The entire aqueous reaction mixture readily undergoes in-flask recycling and thus, represents a sustainable precious metal technology.

Iodine-Triggered Aerobic Oxysulfonylation of Styrenes

An iodine-triggered dioxygen activation in oxysulfonylation reactions of unactivated olefins using sulfonyl hydrazides and iodine as catalyst is reported here. In one pot, near quantitative syntheses of β-hydroxysulfones were achieved at 70 °C, within 7 h, in acetonitrile and under aerobic conditions. A plausible mechanism is established by radical trapping and 18O labelling experiments for the operationally simple, efficient and economically viable transformation. The direct activation of aerial oxygen under metal-free and mild conditions is proposed for the oxysulfonylation of olefins. (Figure presented.).

Palladium-mediated synthesis of 1,1,2-triarylethanes. Application to the synthesis of CDP-840

A three-step protocol toward 1,1,2-triarylethanes 1 starting with β-ketosulfones 2 is developed. A facile process is carried out for the (1) reduction of 2 with NaBH4, (2) BF3·OEt2-mediated Friedel-Crafts reactions of the

Synthesis of γ-sulfonyl δ-lactones and β-sulfonyl styrenes

A facile route to the synthesis of γ-sulfonyl lactones 5 and β-sulfonyl styrenes 6 has been developed, achieving moderate to good yields via the (1) NaH mediated Michael addition of β-ketosulfones 3 and methyl acrylate in refluxing THF and (2) NaBH4mediated stereoselective reduction/lactonization of δ-ketoesters 4 in boiling MeOH, or (3) boron trifluoride etherate mediated ring-opening of lactones 5 in MeOH at reflux.