- Visible Light-Promoted Sulfoxonium Ylides Synthesis from Aryl Diazoacetates and Sulfoxides
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A visible light-promoted reaction of donor/acceptor diazoalkanes with sulfoxides towards the synthesis of synthetically useful sulfoxonium ylides was reported. The reaction occurred under sole visible light irradiation without the need of any transition-metals or additives, affording the corresponding sulfoxonium ylides in moderate to good yields. The success of late-stage modification of natural isolates or drug candidates, scale-up reaction and transformation of sulfoxonium ylides to other useful molecules further rendered the approach valuable.
- Lu, Juan,Li, Lei,He, Xiang-Kui,Xu, Guo-Yong,Xuan, Jun
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- DABCO mediated one pot synthesis of sulfoxonium ylides under blue LED
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DABCO mediated practical and convenient one pot method has been developed to access sulfoxonium ylides under photoredox and metal free conditions at room temperature. The protocol explored the reactivity of DMSO and α-aryl-α-diazo esters in presence of DABCO under blue LED condition. We demonstrated the generality of this protocol by synthesizing a variety of sulfoxonium ylides in very good yields. The practicality of the protocol has been demonstrated by the gram scale synthesis as well as by the extension of this protocol to synthesize precursors of biologically active compounds. This straightforward and practical method offers an alternative route to access very useful sulfoxonium ylides from α-aryl-α-diazoacetates.
- Khade, Vikas V.,Thube, Archana S.,Warghude, Prakash K.,Bhat, Ramakrishna G.
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(2021/07/25)
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- Visible-Light-Mediated Strategies to Assemble Alkyl 2-Carboxylate-2,3,3-Trisubstituted β-Lactams and 5-Alkoxy-2,2,4-Trisubstituted Furan-3(2H)-ones Using Aryldiazoacetates and Aryldiazoketones
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Two new visible-light-mediated strategies are described starting from aryldiazoacetates. The first approach describes their reaction with azides to afford the corresponding imines, and then reaction with aryldiazoketones produces alkyl 2-carboxylate-2,3,3
- Deflon, Victor M.,Dos Santos, Caio Y.,Gallo, Rafael D. C.,Jurberg, Igor D.,Munaretto, Laiéli S.,Okada, Celso Y.
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p. 9292 - 9296
(2021/12/06)
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- An efficient method to prepare sulfoxonium ylides and their reactivity studies using copper powder and Sc(III) as catalysts: Molecular and electronic structure analysis
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Sulfoxonium ylides are the viable alternatives for diazo compounds as carbene precursors. Unlike diazo compounds, these are bench-stable and crystalline solids. However, the existing methods for the synthesis of sulfoxonium ylides have disadvantages related to the yields, substrate scope, and usage of expensive catalysts. Therefore, it is necessary to develop efficient and competitive protocols for the preparation of sulfoxonium ylides. In this study, we developed an economically affordable protocol for the synthesis of sulfoxonium ylides from diazo compounds using copper powder as a catalyst. This protocol leads to the efficient multigram-scale synthesis of a wide range of sulfoxonium ylides in good yields. Further, we demonstrated scandium triflate–catalyzed carbene insertion into the N?H bond from sulfoxonium ylide. A variety of anilines and sulfoxonium ylides with various functional groups reacted well and produced the corresponding α-amino esters in good yields. All the synthesized compounds were characterized using various standard spectroscopic and analytical techniques. We also used computational methods to understand the electronic structure of all the sulfoxonium ylides using geometry optimization, frequency calculation, molecular orbital and natural bond orbital analysis, and energy decomposition analysis. Our computational results revealed that the interaction between carbene and dimethyl sulfoxide is covalent in nature and stable enough to handle in the absence of any catalyst.
- Ramakrishna, Kankanala,Jayarani, Arumugam,Koothradan, Fathima Febin,Sivasankar, Chinnappan
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- Copper-catalyzed N–H insertion reactions from sulfoxonium ylides
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The first use of copper(II) as an efficient catalyst for N–H insertion reactions between anilines and α-carbonyl sulfoxonium ylides is described. Products, 39 arylglycine derivatives, were obtained in yields up to 97% employing a simple and fast experimental procedure.
- Furniel, Lucas G.,Burtoloso, Antonio C.B.
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- Palladium-Catalyzed Synthesis of Bis-Substituted Sulfoxonium Ylides
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The lack of general access to bis-substituted sulfoxonium ylides is addressed by developing a palladium-catalyzed C-H cross-coupling of α-ester sulfoxonium ylides with (hetero)aryl iodides, bromides, and triflates. Three different catalysts have been eval
- Janot, Christopher,Palamini, Pierre,Dobson, Benjamin C.,Muir, James,A?ssa, Christophe
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p. 296 - 299
(2019/01/10)
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- Coupling of Sulfoxonium Ylides with Arynes: A Direct Synthesis of Pro-Chiral Aryl Ketosulfoxonium Ylides and Its Application in the Preparation of α-Aryl Ketones
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A general, mild, and versatile synthesis of the challenging α-aryl-β-ketosulfoxonium ylides has been developed for the first time, substituting traditional methods starting from diazo compounds. The arylation of easily accessible β-ketosulfoxonium ylides using aryne chemistry allowed the preparation of a large scope of the pro-chiral ylides in very good yields (40 examples; up to 85%). As applications, these ylides were smoothly converted into α-aryl ketones after desulfurization in good yields (up to 98%) as well as in other important derivatives.
- Talero, Alexánder Garay,Martins, Bruna Sim?es,Burtoloso, Antonio C. B.
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p. 7206 - 7211
(2018/11/23)
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- Catalyst-Free Insertion of Sulfoxonium Ylides into Aryl Thiols. A Direct Preparation of β-Keto Thioethers
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Insertion of sulfoxonium ylides into the S-H bond of aryl thiols without the need for a catalyst is demonstrated, furnishing β-keto thioethers in excellent yield in most cases. The method overcomes traditional syntheses that employ metal catalysts in combination with diazo compounds or toxic and hard-prepared haloketones. The experimental setup consists of mixing the reagents in acetonitrile at room temperature. Additional experimental as well as kinetic isotopic effect studies give some insight into the mechanism of this reaction.
- Dias, Rafael M. P.,Burtoloso, Antonio C. B.
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supporting information
p. 3034 - 3037
(2016/07/06)
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