34009-05-7Relevant academic research and scientific papers
Alkylation of Nitropyridines via Vicarious Nucleophilic Substitution
Antoniak, Damian,Barbasiewicz, Micha?
supporting information, p. 516 - 519 (2022/01/20)
Electrophilic nitropyridines react with sulfonyl-stabilized carbanions to give products of C-H alkylation via vicarious nucleophilic substitution. The process consists of formation of the Meisenheimer-type adduct followed by base-induced β-elimination of the sulfinic acid (e.g., PhSO2H). Mechanistic studies reveal that in the latter step alkyl substituent and adjacent nitro group tend to planarize for effective stabilization of benzyl anion, and thus, adduct of hindered isopropyl carbanion remains stable toward elimination for steric reasons.
Base-Mediated Radical Borylation of Alkyl Sulfones
Huang, Mingming,Hu, Jiefeng,Krummenacher, Ivo,Friedrich, Alexandra,Braunschweig, Holger,Westcott, Stephen A.,Radius, Udo,Marder, Todd B.
supporting information, (2021/12/02)
A practical and direct method was developed for the production of versatile alkyl boronate esters via transition metal-free borylation of primary and secondary alkyl sulfones. The key to the success of the strategy is the use of bis(neopentyl glycolato) diboron (B2neop2), with a stoichiometric amount of base as a promoter. The practicality and industrial potential of this protocol are highlighted by its wide functional group tolerance, the late-stage modification of complex compounds, no need for further transesterification, and operational simplicity. Radical clock, radical trap experiments, and EPR studies were conducted which show that the borylation process involves radical intermediates.
Cu-mediated: vs. Cu-free selective borylation of aryl alkyl sulfones
Hu, Jiefeng,Huang, Mingming,Marder, Todd B.,Radius, Udo,Tang, Man,Westcott, Stephen A.
supporting information, p. 395 - 398 (2022/01/19)
A Cu-catalysed borylation of aryl alkyl sulfones was developed for the high yield synthesis of versatile arylboronic esters using a readily prepared NHC-Cu catalyst. In addition, the selective cleavage of either alkyl(C)-sulfonyl or aryl(C)-sulfonyl bonds
Stereodivergent synthesis of alkenes by controllable syn-/anti-fragmentation of β-hydroxysulfonyl intermediates
Górski, Bartosz,Basiak, Dariusz,Grzesiński, ?ukasz,Barbasiewicz, Micha?
supporting information, p. 7660 - 7663 (2019/08/30)
The reduction of the carbonyl group in acylated trifluoroethyl alkanesulfonates follows the Felkin-Ahn selectivity, and the so-formed diastereomeric β-hydroxysulfonyl intermediates undergo syn- and anti-fragmentation, depending on the reaction conditions. In effect, isomeric E- and Z-alkenes are formed in a stereodivergent manner, which mimics the mechanistic manifold of the Peterson olefination.
MANUFACTURING METHOD OF COMPOUND HAVING SULFONYL GROUP
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Paragraph 0108; 0109; 0121-0124, (2018/10/03)
The present invention relates to a method for manufacturing a compound having a sulfonyl group, which includes a step for reacting thiosulfonates in a solvent comprising nucleophilic bases with an electrophilic agent. Accordingly, the present invention can manufacture the compound having the sulfonyl group with a variety of structures with high efficiency and high yield through more simplified processes than conventional methods.COPYRIGHT KIPO 2018
A simple route to 1,4-addition reactions by Co-catalyzed reductive coupling of organic tosylates and triflates with activated alkenes
Hsieh, Jen-Chieh,Chu, Yi-Hua,Muralirajan, Krishnamoorthy,Cheng, Chien-Hong
, p. 11584 - 11587 (2017/10/27)
An efficient Co-catalyzed 1,4-addition reaction of alkyl/aryl triflates and tosylates with activated alkenes is described. In this reaction, an air-stable cobalt(ii) complex, a mild reducing agent Zn and a simple proton source (H2O) are used. A radical mechanism for the addition of alkyl tosylates to activated alkenes is likely involved.
Synthesis of Sulfones and Sulfonamides via Sulfinate Anions: Revisiting the Utility of Thiosulfonates
Shyam, Pranab K.,Jang, Hye-Young
, p. 1761 - 1767 (2017/02/10)
Simple and high-yielding strategies for the production of a variety of sulfones and sulfonamides, using thiosulfonates synthesized by copper-catalyzed aerobic dimerization, are reported. Although thiosulfonates are an old class of compound, practical methods for their synthesis and utilization have not been rigorously developed. In this study, we revisit the reactions of easily accessible thiosulfonates to form sulfinate anions. Because of the similar reactivity of thiosulfonates and metal sulfinates derived from toxic SO2, thiosulfinates are proposed to be stable, nontoxic alternatives to metal sulfinate salts.
A molybdenum based metallomicellar catalyst for controlled and selective sulfoxidation reactions in aqueous medium
Chakravarthy, Rajan Deepan,Ramkumar, Venkatachalam,Chand, Dillip Kumar
, p. 2190 - 2196 (2014/04/17)
A surfactant based molybdenum system that exhibits catalytic activity for sulfoxidation reactions of various organic sulfides in aqueous medium has been developed and comprehensively characterized using IR, XRD, NMR, ESI-MS, DLS and TEM. The catalyst showcases remarkable selectivity for the preparation of both sulfoxides and sulfones in the range of good to excellent yields. Furthermore, the catalyst showed a high degree of tolerance towards various sensitive functional groups such as hydroxyl, acetal, aldehyde, amine, imine, oxime, cyano and alkene. the Partner Organisations 2014.
Investigation of steric and electronic effects in the copper-catalysed asymmetric oxidation of sulfides
O'Mahony, Graham E.,Eccles, Kevin S.,Morrison, Robin E.,Ford, Alan,Lawrence, Simon E.,Maguire, Anita R.
, p. 10168 - 10184 (2013/11/06)
Steric and electronic effects in the copper-catalysed asymmetric oxidation of aryl benzyl, aryl alkyl and alkyl benzyl sulfides have been investigated. The presence of an aryl group directly attached to the sulfur is essential to afford sulfoxides with high enantioselectivities, with up to 97% ee for 2-naphthyl benzyl sulfoxide, the highest enantioselectivity achieved to date for copper-catalysed asymmetric sulfoxidation. In contrast, the benzyl substituent can be replaced by sterically comparable groups with no effect on enantioselectivity. Copper-mediated oxidation of substituted aryl benzyl sulfides display modest steric and electronic effects resulting in comparable or lower enantioselectivities to those obtained with the unsubstituted benzyl phenyl sulfide.
Iron-catalyzed desulfinylative C-C cross-coupling reactions of sulfonyl chlorides with grignard reagents
Rao Volla, Chandra M.,Vogel, Pierre
, p. 1305 - 1307 (2008/12/22)
(Chemical Equation Presented) A friendly couple: Conditions have been uncovered that allow the desulfinylative C-C cross-coupling reaction of inexpensive sulfonyl chlorides and Grignard reagents (see scheme, acac = acetylacetonate, NMP = N-methylpyrrolidone). The reactions rely on environmentally friendly iron catalysts and do not require expensive and/or toxic ligands.
