Sulfonyl reaction

Methanesulfonic and ben2enesulfonic anhydrides are the most frequently used anhydrides ia Friedel-Crafts sulfonylation reactions ... 

IV-Sulfonylation. The /V-sulfonylation reaction (Scheme 42) was performed using different sulfonyl chlorides and some enantiopure sulfonamido derivatives were synthesized.54 The TV-selectivity of sulfonylation was ascertained by 13C NMR.62... 

Selected entries from Methods in Enzymology [vol, page(s)] Sulfonylation reaction, 11, 706 reaction kinetics, 11, 707 second-order rate constants for inactivation of chymotrypsin, trypsin, and acetylcholine esterase by PMSE and related sulfonylat-ing agents, 11, 707 reactivation of PMS-chymotrypsin, 11, 710 as inhibitor [of calcium-activated factor, 80, 674 of cathepsin G, 80, 565 of crayfish trypsin, 80, 639 of elastase, 80, 587 of pro-lylcarboxypeptidase, 80, 465 of protease Re, 80, 691 of protease So, 80, 695 of protein C, 80, 329] proteolysis, 76, 7. 

Friedel-Crafts (FC) alkylation, acylation, and sulfonylation reactions are important C-C or C-S bond forming reactions in organic chemistry [60-64], Since the seminal works of Charles Friedel and James Mason Crafts published in 1877 in which they report the use of A1C13 for alkylation reactions [65], the search for more active catalysts, especially for acylation reactions, continues. Due to increasing environmental concerns, the need for green catalysts and processes for the FC reaction has gained significant importance. Bi(III) salts have shown to be efficient and recoverable catalysts with applicability in this area [13]. 

Scheme II Mechanism for the sulfonylation reaction catalyzed by BifOTfb xlLO...

To mechanically stirred, cooled (0°C) chlorosulfonic acid (70 mL, 1.05 mol) was added the crude acetamidosulfonamide (29.7 g, 0.114 mol 93 7 trans/cis) portionwise at a rate to maintain the internal temperature <20°C. The dark sulfonylation reaction mixture was heated to 50°C for 12 h, or until the reaction was judged to be complete by HPLC. During the reaction hydrogen chloride (0.114 mol) was evolved. 

Assay Procedure An aliquot (0.1 mL) is diluted to 100.0 mL with H20 and then analyzed by the following HPLC method. Instrument Spectra Physics 8800. Column 4.1 times 250 mm Ultrasphere C-8 (Altex Inc.). Eluent A H20 (0.1% v/v H3PO4). Eluent B MeCN. Gradient 97 3 to 35 65 A B over 25 min. Flow Rate 2.0 mL/min. Temperature 45°C. Injection 10.0 nL. Detection UV (230 nm). Retention Times Sulfonic Acid (cis/trans isomers) 5.0 min, Acetamidosulfone (cis isomer) 9.0 min, Acetamidosulfone (trans isomer) 10.0 min. The sulfonylation reaction was considered to be complete when less than 1% of acetamidosulfone (vs. the sulfonic acid - 6-methyl-7,7-dioxo-4,5,6,7,-... 

Polysulfones can be prepared by Friedel-Crafts sulfonylation reactions [133-150]. The carbenium ion intermediates can be generated from the Lewis acid-catalyzed reaction of involving arene sulfonyl chloride [Eq. 

Lewis acids such as A1C13, AlBr3, FeCl3, and SbCl5 have been used [151]. Friedel-Craft sulfonylation reactions typically require more than one mole equivalent of Lewis acid per sulfonyl halide. This is apparently due to the coordination of one equivalent of the Lewis acid with the sulfonyl group. 

Le Roux, C., Dubac, J. Bismuth(lll) chloride and triflate novel catalysts for acylation and sulfonylation reactions. Survey and mechanistic aspects. Synlett2002, 181-200. 

Compounds with functional groups at this 3-position have been shown to have affinity for galectins. For example, Sorme et al. synthesized 12 N-acetyllactosamine (LacNAc, 1) derivatives with C3 functionalization. Specifically, they generated a 3 -deoxy-3 -amino lactosamine derivative, which could be further modified via N-acylation or N-sulfonylation reactions [52], These compounds were tested for their ability to bind to galectin-3, a lectin proposed to participate in the formation of the immunological synapse between T cells and antigen-presenting cells [94]. Compounds with inhibitory... 

Stoodley and Whiting144 have reported O-mesylation of a bicyclic heterocyclic alcohol with mesyl chloride and triethylamine in dichloromethane (presumably via the sulfene) and N-mesylation of the same substrate with mesyl chloride in pyridine whether the latter product arises via direct displacement or some other route does not appear to have been determined. These and other results in this paper show the sensitivity of the sulfonylation reactions to the precise conditions, a feature that could lead to opportunity in one situation and difficulty in another. 

Fiori KW, Puchlopek ALA, Miller SJ (2009) Enantioselective sulfonylation reactions mediated by a tetrapeptide catalyst. Nat Chem 1 630-634... 

Various synthetic approaches have been demonstrated for the synthesis of PAEs since early days [35 0], PAEs were synthesized by Ullmann condensation between bisphenols and aryl fcis-halide monomers using Cu(I) salt/pyridine as catalyst [36], General Electric developed the first commercially successful PAE poly(2,6-dimethyl phenylene oxide) (PPO) [38], It was prepared by oxidative coupling of 2,6-dimethyI phenol. However, this process has its own restrictions, because it does not allow much structural variation or inclusion of any electron-withdrawing group into the polymer main chain. First attempts to synthesize polysulfones (PSF) were successfully done by Friedel-Crafts sulfonylation reaction of arylenedisulfonyl chlorides, for example, diphenyl ether-4,4 -disulfonyl chloride with diaryl ethers, for example, diphenyl ether, or by self-condensation of 4-phenoxy benzene sulfonyl chloride in the presence of FeCls [41], Whereas the former reaction involves side reactions (sulfonylation not only in the para- but also in the ort/io-position), the latter produces only the desired linear all-para products. 

The imidazolium chloroaluminate ionic liquid was also found to be effective as an unconventional reaction media and as Lewis acid catalyst for the Friedel-Crafts sulfonylation reaction of benzene and substituted benzene with p-toluenesulfonyl chloride giving rise to the diarylsulfones in high yield (Scheme 6.14) [16]. 

Direct preparation of aryl sulfonyl chlorides from arenes has been achieved through electrophilic aromatic substitution with excess chlorosulfonic acid. ° This method was used in the initial medicinal chemistiy route for the preparation of Viagra, which relied on a penultimate chloro-sulfonylation reaction with chlorosulfonic acid (Scheme 13.3). ... 

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