Copper-catalyzed aerobic oxidation and cleavage/formation of C–S bond: a novel synthesis of aryl methyl sulfones from aryl halides and DMSO

Yuan, Gaoqing; Zheng, Junhua; Gao, Xiaofang; Li, Xianwei; Huang, Liangbin; Chen, Huoji; Jiang, Huanfeng

doi:10.1039/c2cc32964f

Cited by 116 publications

(36 citation statements)

References 35 publications

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“…However, the troublesome compatibility of the stoichiometric amount of oxidant and harsh reaction conditions in these processes might be the major challenges. [4] During our search for more selective aerobic oxidative transformations, [5] we reasoned that a copper/carbene species could be a versatile precursor in such conversions. Herein, we would like to present an example of ketoneto-alkyne (via hydrazones) transformation by selective deprotonation in the presence of O 2 .…”

mentioning

confidence: 99%

Copper‐Catalyzed Aerobic Oxidative Transformation of Ketone‐Derived N‐Tosyl Hydrazones: An Entry to Alkynes

Li¹,

Liu²,

Chen³

et al. 2014

Angew Chem Int Ed

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A novel strategy involving Cu-catalyzed oxidative transformation of ketone-derived hydrazone moiety to various synthetic valuable internal alkynes and diynes has been developed. This method features inexpensive metal catalyst, green oxidant, good functional group tolerance, high regioselectivity and readily available starting materials. Oxidative deprotonation reactions were carried out to form internal alkynes and symmetrical diynes. Cross-coupling reactions of hydrazones with halides and terminal alkynes were performed to afford functionalized alkynes and unsymmetrical conjugated diynes. A mechanism proceeding through a Cu-carbene intermediate is proposed for the CC triple bond formation.

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confidence: 99%

Copper‐Catalyzed Aerobic Oxidative Transformation of Ketone‐Derived N‐Tosyl Hydrazones: An Entry to Alkynes

Li¹,

Liu²,

Chen³

et al. 2014

Angew Chem Int Ed

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“…287 Aryl methyl sulfones 44 are obtained via CuO 2 -catalyzed oxidation and cleavage/formation of carbon-sulfur bond from aryl halides and DMSO (Scheme 32). 288 After first oxidation of DMSO to the corresponding sulfone, the reactive complex 43 has been suggested to be involved in the formation of sulfone 44. Sulfoxides undergo photochemical oxidation to sulfones in variable yield.…”

Section: Oxidation Of Sulfoxides To Sulfones By Miscellaneous Methodsmentioning

confidence: 99%

7.28 Oxidation of Sulfur, Selenium, and Tellurium

Lattanzi

2014

Comprehensive Organic Synthesis II

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“…23 Ionic liquids (ILs) are a fascinating class of solvent that have been widely embraced by the catalysis community as a method for immobilization of catalysts under homogeneous, liquid-liquid biphasic and liquid-solid (SILP) biphasic conditions. 24 Recent relevant examples include an efficient protocol for the oxidation of sulfides to sulfones catalyzed by V 2 O 5 in [C 12 mim] [HSO 4 ], 25 highly selective sulfoxidation of sulfides to sulfoxides catalysed by the bifunctional IL combination [SO 3 HC 3 py][TiF 6 ]/[C 4 py] [BF 4 ], 26 a selective catalyst-free oxidation of sulfides to sulfoxides that is faster in ionic liquid than conventional solvents, 27 and, most recently, heterogeneous selective oxidation of sulfides catalysed by ionic liquid-based polyoxometalates 28 or tungstate-based poly(ionic)liquid entrapped magnetic nanoparticles. 29 While good conversions and high selectivities have been obtained In IL media, surprisingly few recycle studies have been reported.…”

Section: Introductionmentioning

confidence: 99%

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

et al. 2015

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ARTICLE This journal isThe peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP has been prepared by an anion exchange of ring opening metathesisderived pyrrolidinium-decorated norbornene/cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO 4 {WO(O 2 ) 2 } 4 ]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46,428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst . IntroductionThe selective oxidation of sulfides is a challenging and technologically important process as sulfoxides and sulfones are versatile intermediates used in the synthesis of fine chemicals, bioactive compounds, agrochemicals, 1 as chiral auxiliaries 2 and most recently as ligands for transition metal asymmetric catalysis. 3 Moreover, sulfide oxidation is also the basis for the catalytic oxidative desulfurisation of crude oil in which sulfur compounds are removed by selective extraction of their sulfones into a polar solvent under much milder conditions than typically required for classical industrial catalytic hydrodesulfurization. 4 Sulfoxidations have traditionally employed either strong oxidants, (e.g. nitric acid or KMnO 4 ) which suffer numerous drawbacks such as low yields, extreme reaction conditions and poor E-factors, 5 or reagents such as mchloroperbenzoic acid, 6 UHP, 7 NaClO, 8 NaIO 4 , 9 oxone 10 and dimethyldioxirane 11 which are expensive, must be used in excess, generate stoichiometric amounts of by-product and involve protocols that require long reaction times, high temperatures and complicated handling procedures. Since hydrogen peroxide is economical, more environmentally benign and relatively atom efficient it is considered the oxidant of choice and as such numerous organocatalysts, 12 enzymes 13 as well as transition metal catalysts based on iron, 14 manganese, 15 vanadium, 16 titanium, 17 ruthenium, 18 molybdenum, 19 tungsten, 20 and zinc 21 have been developed for this process. In this regard, an efficient catalyst must be highly selective for either sulfone or sulfoxide, inexpensive, easy to prepare and handle, operate under mild conditions across a wide range of substrates and functionality, have long term stability and be easy to recover and recycle. While several of these criteria have been successfully realized there is still a demand to identify and develop alternative systems to address remaining drawbacks ...

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Copper-catalyzed aerobic oxidation and cleavage/formation of C–S bond: a novel synthesis of aryl methyl sulfones from aryl halides and DMSO

Cited by 116 publications

References 35 publications

Copper‐Catalyzed Aerobic Oxidative Transformation of Ketone‐Derived N‐Tosyl Hydrazones: An Entry to Alkynes

Copper‐Catalyzed Aerobic Oxidative Transformation of Ketone‐Derived N‐Tosyl Hydrazones: An Entry to Alkynes

7.28 Oxidation of Sulfur, Selenium, and Tellurium

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

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