21272-85-5Relevant academic research and scientific papers
Reactivity, Selectivity, and Stability in Sulfenic Acid Detection: A Comparative Study of Nucleophilic and Electrophilic Probes
Gupta, Vinayak,Paritala, Hanumantharao,Carroll, Kate S.
, p. 1411 - 1418 (2016/06/09)
The comparative reaction efficiencies of currently used nucleophilic and electrophilic probes toward cysteine sulfenic acid have been thoroughly evaluated in two different settings-(i) a small molecule dipeptide based model and (ii) a recombinant protein model. We further evaluated the stability of corresponding thioether and sulfoxide adducts under reducing conditions which are commonly encountered during proteomic protocols and in cell analysis. Powered by the development of new cyclic and linear C-nucleophiles, the unsurpassed efficiency in the capture of sulfenic acid under competitive conditions is achieved and thus holds great promise as highly potent tools for activity-based sulfenome profiling.
General allylic C-H alkylation with tertiary nucleophiles
Howell, Jennifer M.,Liu, Wei,Young, Andrew J.,White, M. Christina
supporting information, p. 5750 - 5754 (2014/05/06)
A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.
A simple synthesis of some new arylsulfonylnitromethanes
Aleksiev,Ivanova,Valeva
experimental part, p. 743 - 747 (2012/06/18)
Arylsulfonylnitromethanes were obtained by a nucleophilic substitution reaction. The suggested method of obtaining arylsulfonylnitromethanes has some important advantages over the methods known so far: It is a relatively short, one-stage process; no byproducts are obtained, so there is no need for further procedures to separate the main products from thereaction mixture; and the final compounds possess a good degree of purity. The structure of the new products were confirmed by 1H NMR, IR, and elemental analysis. The solid state structure of 6 was established by X-ray analysis. Copyright
Enantioselective synthesis of α-stereogenic γ-keto esters via formal umpolung
Prakash, G. K. Surya,Wang, Fang,Zhang, Zhe,Ni, Chuanfa,Haiges, Ralf,Olah, George A.
supporting information; experimental part, p. 3260 - 3263 (2012/09/08)
A feasible method has been developed for the enantioselective synthesis of α-stereogenic γ-keto esters. By employing nitro(phenylsulfonyl) methane as an acyl anion equivalent, the integrated Michael addition reaction-oxidative methanolysis protocol allows the preparation of various γ-keto esters with high optical purities.
Reactions of (1-nitroethenyl)sulfonylbenzene, a nitroethene derivative geminally substituted by a second W-group
Wade, Peter A.,Murray, James K.,Pipic, Alma,Arbaugh, Robert J.,Jeyarajasingam, Amutha
body text, p. 337 - 342 (2010/04/30)
Nitroaldol reaction of phenylsulfonylnitromethane with formaldehyde affords a mixture of 2, 4-dinitro-2, 4-bis (phe-nylsulfonyl)butan-1-ol and 2, 4-dinitro-2, 4- bis (phenylsulfonyl)pentane-1, 5-diol. Treatment of this mixture with base followed by reacidification affords 1,1′-[(1, 3-dinitro-1, 3-propanediyl)bis (sulfonyl)]bis (benzene) as a mixture of (R*, R*) and (R*, S*)- diastereomers from which the (R*, S*)- diastereomer can be obtained pure. The intermediate in the nitroaldol reaction is (1-nitroethenyl)sulfonylbenzene and, if dienes are present, additional products are also obtained. If either (E)-2-methyl-1, 3-pentadiene or 1-(1-methylethenyl)cyclohexene are present, typical Diels-Alder adducts are obtained with the major isomers explainable by assuming a transition state in which the nitro group is endo. If furan is present, its formal conjugate addition product, 2-[2-nitro-2-(phenylsulfonyl)ethyl]furan, is formed. If cyclooctatetraene is present, it first dimerizes and then affords isomeric Diels-Alder cycloadducts of the dimer. Semiempirical calculations comparing the LUMO energies of (1-nitroethenyl)sulfonylbenzene to the corresponding trans-1,2 isomer are presented to explain relative reactivity of 1, 1- and 1, 2-disubstituted dienophiles. Copyright
Oxidation of azides by the HOF·CH3CN: A novel synthesis of nitro compounds
Carmeli, Mira,Rozen, Shlomo
, p. 4585 - 4589 (2007/10/03)
The HOF·CH3CN complex, readily prepared by passing F 2 through aqueous acetonitrile, is an exceptionally efficient oxygen transfer agent. It is unique in its capacity to oxidize various azides into the corresponding nitro derivatives. This method requires short reactions times and room temperature or below, and the desired nitro compounds were usually isolated in very good yields. The respective nitroso derivatives are believed to be the intermediates in this reaction. Functional groups such as aromatic rings, ketones, nitriles, halides, alcohols, and esters are tolerated. Sulfides react with HOF·CH3CN usually at the same rate as azides. Amines and olefins, however, react faster, so they have to be protected first. Nitro derivatives with various oxygen isotopes can be made using the labeled H 18OF·CH3CN. In the case of chiral azides the stereochemistry around the nitrogen-bonded carbons is retained.
α-NITRO SULFONES. 2. CONVENIENT NEW SYNTHESIS AND SELECTED FUNCTIONAL GROUP TRANSFORMATIONS
Wade, Peter A.,Hinney, Harry R.,Amin, Nayan V.,Vail, Peter D.,Morrow, Scott D.,et al.
, p. 765 - 770 (2007/10/02)
(Phenylsulfonyl)nitromethane (1) is preferentially C-alkylated by benzylic halides and primary alkyl iodides, affording secondary α-nitro sulfone products. α-Nitro sulfones are also obtained from the corresponding C-alkylation of allylic acetates in the presence of catalytic tetrakis(triphenylphosphine)palladium.The palladium(0)-catalyzed reaction is stereospecific for geranyl and neryl acetates and is also regioselective.Desulfonation of α-nitro sulfones is readily accomplished by light-induced reduction with 1-benzyl-1,4-dihydronicotinamide (BNAH).Reduction of secondary α-nitro sulfones with 20percent aqueous titanium(III) chloride affords nitriles.Oxidation with alkaline permanganate affords carboxylic acids.
Synthesis of methyl trans‐oxazolidine‐5‐carboxylate, a chiral synthon for threo‐β‐amino‐α‐hydroxy acid
Seo, Youngran,Lee, Yoonjae,Lee, Boram,Kim, Bonghyun,Kim, Young Gyu
, (2019/04/04)
Procedures yielding phenylsulfonylnitromethane as white powder and 3‐tert‐butyl 5‐methyl (4S,5R)‐4‐benzyloxazolidine‐3,5‐dicarboxylate as pure product are presented. A single‐necked, round‐bottomed flask equipped with a Teflon‐coated, oval magnetic stir bar is primarily used. Notes on the paraphernalia and chemicals to be used during each procedures are provided. The chapter concludes with a brief discussion on stereoselective syntheses of vicinal amino hydroxy acids.
