- Synthesis of sulfone derivatives via palladium-catalyzed cross-coupling of benzyl trimethylammonium triflates and sulfonyl hydrazides
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A palladium-catalyzed cross-coupling of benzyl trimethylammonium triflates and sulfonyl hydrazides for the synthesis of various benzyl sulfones is reported. This novel protocol shows widespread functional group tolerance, leading to the desired sulfones in moderate to excellent yields.
- Luo, Jin,Wan, Juelin,Wang, Tao,Yu, Weijie
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supporting information
(2021/12/31)
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- Silver-Catalyzed C(sp3)-H Sulfonylation for the Synthesis of Benzyl Sulfones Using Toluene Derivatives and α-Amino Acid Sulfonamides
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We describe a simple and practical protocol for the synthesis of benzyl sulfones using readily available toluene derivatives and α-amino acid sulfonamides. The reaction proceeds to afford a broad range of benzyl sulfones in moderate to high yields under silver catalysis. The mechanism possibly involves a Minisci-type formation of α-aminoalkyl radical, homolytic cleavage of a N-S bond to generate a sulfonyl radical, and coupling of sulfonyl radical with a benzyl radical formed via hydrogen abstraction by sulfate anion radical. The practicality of the present reaction is demonstrated by a gram-scale synthesis and one-step synthesis of anticancer-active compound. The mechanism studies are conducted using radical scavengers and deuterated toluene.
- Kanyiva, Kyalo Stephen,Shibata, Takanori,Uchida, Kanako
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p. 1377 - 1384
(2021/06/06)
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- Visible-Light-Catalyzed in Situ Denitrogenative Sulfonylation of Sulfonylhydrazones
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A photocatalyzed in situ denitrogenative sulfonylation of N-arylsulfonyl hydrazones has been developed. This transformation provides a low-carbon strategy to assemble arylalkyl sulfones in a stepwise denitrogenation/sulfonylation manner.
- Huang, Xiang,Chen, Xing,Xie, Haisheng,Tan, Zheng,Jiang, Huanfeng,Zeng, Wei
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p. 6784 - 6788
(2021/09/08)
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- A general and practical sulfonylation of benzylic ammonium salts with sulfonyl hydrazides for the synthesis of sulfones
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A practical and efficient approach adopting transition-metal-free cross-coupling of sulfonyl hydrazides with benzyl ammonium salts has been developed to synthesize benzyl sulfones using Cs2CO3 as base under mild conditions. The protocol employs stable and easy to handle coupling partners, and is endowed with good substrate compatibility, leading to functional benzyl sulfones in good yields.
- Zhu, Haibo,Zhang, Yingying,Liu, Yishuai,Yang, Liu,Xie, Zongbo,Jiang, Guofang,Le, Zhang-Gao
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- Sodium Arenesulfinates-Involved Sulfinate Synthesis Revisited: Improved Synthesis and Revised Reaction Mechanism
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Reaction of alcohols with sodium arenesulfinates could afford either sulfones or sulfinates, and O-attack of sulfinate anions onto the in situ generated carbocation intermediates from alcohols was the previous proposed reaction mechanism in many syntheses of sulfinates. This concept, which is often used consciously or unconsciously, was revised herein by using isotopic labeling experiments and development of an improved sulfinate synthesis. The improved sulfinate synthetic protocol possesses many advantages such as a high sulfinate/sulfone selectivity, a broad substrate scope, metal-free, and mild reaction conditions. The revised reaction mechanism necessitates revision of many previous proposed reaction mechanisms in literatures.
- Ji, Yuan-Zhao,Li, Hui-Jing,Zhang, Jin-Yu,Wu, Yan-Chao
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p. 1846 - 1855
(2019/02/14)
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- Substrate- and temperature-controlled divergence in reactions of alcohols with TosMIC catalyzed by BF3 · Et2O: Facile access to sulfinates and sulfones
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An efficient BF3 · Et2O-catalyzed divergent synthesis of sulfinate esters and sulfones through C–O and C–S bond formation has been achieved from alcohols and p-toluenesulfonylmethyl isocyanide (TosMIC). Various alcohols reacted smoothly with TosMIC under the present conditions at room temperature providing sulfinate esters exclusively. By tuning the reaction temperature, the alcohols that provide highly stabilized carbocation in the reaction medium afforded sulfones as sole products. This study was aimed at understanding the regioselectivity of ambidentate sulfinate ion and to elucidate the interpretation of sulfinate/sulfone scaffolds.
- Pogaku, Naresh,Krishna, Palakodety Radha,Prapurna, Y. Lakshmi
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supporting information
p. 1239 - 1249
(2017/07/06)
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- Palladium Catalyzed Monoselective α-Arylation of Sulfones and Sulfonamides with 2,2,6,6-Tetramethylpiperidine·ZnCl·LiCl Base and Aryl Bromides
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A palladium catalyzed Negishi-type α-arylation of sulfones and sulfonamides with a broad range of aryl bromides has been developed. The substrates are selectively metalated in situ with tmp·ZnCl·LiCl base (tmp: 2,2,6,6-tetramethylpiperidine) and cross-coupled in the presence of a catalyst system that is generated from Pd(dba)2 and XPhos. Electron-deficient, electron-rich, and heterocyclic aryl bromides have been successfully cross-coupled, and sensitive functional groups are well tolerated. Simple aryl bromides are converted overnight at 60 °C in THF while heteroaryl bromides are efficiently coupled within 2 h at 130 °C in a microwave reactor. The desired monoarylated α-branched benzyl sulfones and sulfonamides were obtained in good yields, and overarylation was not detected. The procedure is ideal for late stage functionalization in parallel medicinal chemistry.
- Knauber, Thomas,Tucker, Joseph
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p. 5636 - 5648
(2016/07/14)
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- Iron(III) phthalocyanine-chloride-catalyzed synthesis of sulfones from sulfonylhydrazones
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In this study, sulfones are synthesized from sulfonylhydrazones catalyzed by iron(III) phthalocyanine chloride. This reaction offers broad substrate scope, occurs under mild conditions, utilized readily available reactants, and forms products in good-to-h
- Zhao, Jun-Long,Guo, Shi-Huan,Qiu, Jun,Gou, Xiao-Feng,Hua, Cheng-Wen,Chen, Bang
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supporting information
p. 2375 - 2378
(2016/05/19)
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- One-pot synthesis of multifunctionalized cyclopropanes
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A facile one-step synthetic protocol toward multifunctionalized cyclopropanes 4 is developed from substituted chalcones 1 and sulfones 2 in good yields via a [2C+1C] annulation.
- Chang, Meng-Yang,Chen, Yi-Chia,Chan, Chieh-Kai
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p. 2257 - 2263
(2014/03/21)
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- Synthesis of sulfones by iron-catalyzed decomposition of sulfonylhydrazones
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The Fe-catalyzed decomposition of sulfonylhydrazones gives rise to sulfones. The reaction is quite general and allows the preparation of sulfones from a variety of aryl, alkyl, and α,β-unsaturated aldehydes and ketones. Crossover experiments reveal that the reaction is an intermolecular process, which may proceed by nucleophilic attack of the sulfinate anion on an iron carbene complex. Carbonyl compounds can be easily transformed into sulfones by Fe-catalyzed decomposition of the corresponding sulfonylhydrazones. The process most likely proceeds through an iron carbene complex and opens the door for the design of othernovel Fe-catalyzed reductive couplings. Copyright
- Barluenga, Jose,Tomas-Gamasa, Maria,Aznar, Fernando,Valdes, Carlos
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experimental part
p. 1520 - 1526
(2011/04/25)
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- Iron (III) chloride-catalyzed direct sulfonylation of alcohols with sodium arenesulfinates
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A new protocol for the direct sulfonylation of benzylic, allylic and homoallylic alcohols with sodium arenesulfinates is described by using iron (III) chloride as a catalyst and chlorotrimethylsilane as an additive. This method requires no preactivation o
- Reddy, M. Amarnath,Reddy, P. Surendra,Sreedhar
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supporting information; experimental part
p. 1861 - 1869
(2010/10/21)
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- Stereoselective control by face-to-face versus edge-to-face aromatic interactions: The case of C3-TiIV amino trialkolate sulfoxidation catalysts
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The stereoselective oxidation of differently functionalised benzyl phenyl sulfides has been examined by using enantiopure TiIV trialkanolamine complexes. These complexes efficiently catalyse the sulfoxidation with good stereoselectivities. The
- Santoni, Gabriella,Mba, Miriam,Bonchio, Marcella,Nugent, William A.,Zonta, Cristiano,Licini, Giulia
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experimental part
p. 645 - 654
(2010/05/18)
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- Palladium-catalyzed benzylic direct arylation of benzyl sulfones with aryl halides
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An effective palladium catalyst system for the direct arylation of benzyl sulfones with aryl halides has been developed. The catalytic reaction provides a facile route to diarylmethyl sulfones. The products can be transformed further via desulfonylative functionalization mediated by aluminum compounds.
- Niwa, Takashi,Yorimitsu, Hideki,Oshima, Koichiro
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experimental part
p. 1971 - 1976
(2009/08/07)
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- Asymmetric synthesis of aryl benzyl sulfoxides by vanadium-catalysed oxidation: A combination of enantioselective sulfide oxidation and kinetic resolution in sulfoxide oxidation
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Enantioselective vanadium-catalysed oxidation of aryl benzyl sulfides using Bolm's procedure is accompanied by kinetic resolution in the oxidation of the resulting sulfoxides which enhances the enantiopurities of the sulfoxides recovered (typically >90% ee), albeit with an associated reduction in yield. The effects of ligand, solvent and reaction conditions are discussed in detail. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Kelly, Padraig,Lawrence, Simon E.,Maguire, Anita R.
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p. 4500 - 4509
(2007/10/03)
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- Kinetic resolution in vanadium-catalyzed sulfur oxidation as an efficient route to enantiopure aryl benzyl sulfoxides
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Enantiopure aryl benzyl sulfoxides can be prepared using vanadium-Schiff base catalyzed sulfide oxidation and kinetic resolution of the resulting sulfoxide. The kinetic resolution can be effected in combination with asymmetric sulfide oxidation or instead starting from the racemic sulfoxide. Georg Thieme Verlag Stuttgart.
- Kelly, Pádraig,Lawrence, Simon E.,Maguire, Anita R.
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p. 1569 - 1573
(2007/10/03)
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- Transformation of carbonates into sulfones at the benzylic position via palladium-catalyzed benzylic substitution
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(Chemical Equation Presented) The nucleophilic substitution of benzylic carbonates with sodium arenesulfinates was catalyzed by the palladium complex generated in situ from [Pd(η3-C3H5)Cl] 2 and DPEphos [bis(2-diphenylphosphinophenyl)ether]. The catalytic reaction proceeded in DMSO at 80°C and gave a variety of benzylic sulfones in high yields.
- Kuwano, Ryoichi,Kondo, Yutaka,Shirahama, Tsuyoshi
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p. 2973 - 2975
(2007/10/03)
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- Palladium-Catalyzed Cross-Coupling of Organostannanes with Sulfonyl Chlorides: A Simple Synthesis of Sulfones
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The palladium-catalyzed cross-coupling reaction between aryl- and alkylsulfonyl chlorides and substituted vinyl- and allylstannanes proceeds smoothly to provide good yields of sulfones and tolerates a wide variety of functionalities.
- Labadie, Sharada S.
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p. 2496 - 2498
(2007/10/02)
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