Metal-Free Oxidative Esterification of Ketones and Potassium Xanthates: Selective Synthesis of α-Ketoesters and Esters

Luο, Xingguang; He, Runfa; Liu, Qiang; Gao, Yanping; Li, Jingqing; Chen, Xiuwen; Zhu, Zhongzhi; Huang, Yubing; Li, Yibiao

doi:10.1021/acs.joc.9b03272

Cited by 15 publications

(6 citation statements)

References 76 publications

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“…The α-ketoesters are biologically active compounds that have significant applications in the pharmaceutical industry and serve as an important intermediates and precursors in organic synthesis. [645][646][647][648][649][650][651][652][653][654][655][656] Luo and colleagues [657] have developed a novel method for the synthesis of α-ketoesters by replacing the traditional use of iron, cobalt, and rhodium catalysts and transmetalation with the use of four equivalents of molecular iodine (Scheme 64). [658][659][660][661] By using acetophenone and potassium ethyl xanthate as model substrates, the researchers successfully obtained the desired products in a high yields of up to 87 %.…”

Section: Oxidationmentioning

confidence: 99%

Iodine and DMSO as Surrogate of Hazardous Metal and Non‐Metal Reagents in Organic Synthesis

Reetu,

Kalita,

Dash

et al. 2024

ChemistrySelect

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Organic synthesis involves the production of important chemical structures using scalable and cost‐effective methods that are also environmentally friendly. In this review, a detailed analysis of the use of iodine and DMSO in various synthetic routes for the preparation of valuable targets are presented. These methods reduce the acceptance on expensive additives and reagents, and offer a more sustainable solution for the synthesis of these important chemical scaffolds.

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Section: Oxidationmentioning

confidence: 99%

Iodine and DMSO as Surrogate of Hazardous Metal and Non‐Metal Reagents in Organic Synthesis

Reetu,

Kalita,

Dash

et al. 2024

ChemistrySelect

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“…To the best of our knowledge, the sole attempt to directly transform xanthates into dialkyl thioethers was reported by Degani et al They obtained only small amounts of the desired dialkyl thioethers via the sulfurization of alkyl halides using EtOCS2K as a sulfurizing agent [38]. Based on our research on the development of xanthate chemistry (Scheme 1df) [39][40][41], we herein report a facile approach for use in generating various dialkyl thioethers and aryl thioethers. This approach involves the sulfuration of alkyl halides and aryl halides using ROCS2K as a thiol-free sulfurizing and alkylating reagent (Scheme 1g).…”

Section: Introductionmentioning

confidence: 99%

Expedient Syntheses of Alkyl and Aryl Thioethers using Xanthates as Thiol-Free Reagents

Nie,

He,

Xie

et al. 2024

Preprint

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Thioethers are critical in the fields of pharmaceuticals and organic synthesis, but most of the methods for synthesizing alkyl thioethers employ foul-smelling thiols as starting materials or generate them as by-products. Additionally, most thiols are air-sensitive and are easily oxidized to produce disulfides under atmospheric conditions; thus, a novel method for synthesizing thioethers is necessary. This paper reports a simple, effective, green method for synthesizing dialkyl or alkyl aryl thioether derivatives using odorless, stable, low-cost ROCS2K as a thiol surrogate. This transformation offers a broad substrate scope and good functional group tolerance with excellent selectivity. The reaction likely proceeds via xanthate intermediates, which can be readily generated via the nucleophilic substitution of alkyl halides or aryl halides with ROCS2K under transition-metal-free and base-free conditions.

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“…They are used as collectors in flotation processes where their function is to create a hydrophobic layer around the mineral particle promoting the particle’s adhesion to air bubbles [ 1 ]. Xanthates are also used as precursors in a variety of different chemical syntheses [ 2 – 4 ]. However, xanthates and especially their decomposition product, carbon disulfide (CS 2 ), are hazardous to the environment.…”

Section: Introductionmentioning

confidence: 99%

The effect of experimental conditions on the formation of dixanthogen by triiodide oxidation in the determination of ethyl xanthate by HPLC–ICP-MS/MS

et al. 2022

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The rising concern over the environmental impact of xanthates, especially in the arctic region, has increased the need to study these traditional flotation reagents in greater detail. The environmental concern relates mostly to the formation of carbon disulfide (CS2) and the heavy metal complexes of xanthates. Due to the unstable nature and multiple reaction mechanisms of xanthates, their reliable determination at low concentration levels is difficult. In this study, a xanthate pretreatment method was optimized and applied for the determination of ethyl xanthate (EX−) by high performance liquid chromatography–inductively coupled plasma tandem mass spectrometry (HPLC–ICP-MS/MS). Ethyl xanthate was oxidized to diethyl dixanthogen ((EX)2) by triiodide (I3−) in aqueous solution and the formed (EX)2 was extracted into n-hexane. Important experimental parameters, including pH, I3− amount, and oxidation time, were optimized and the detection limit of 0.29 mg L−1 for potassium ethyl xanthate was obtained. During the optimization experiments, it was found that the oxidation reaction resulted in multiple products, decreasing the efficiency of (EX)2 formation and, therefore, the sensitivity of the method. The proposed method was applied to wastewater samples with recoveries of 105–106%. This study provides a selective method for the determination of ethyl xanthate and introduces novel information on the parameters affecting the oxidation of xanthates. Graphical abstract

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Metal-Free Oxidative Esterification of Ketones and Potassium Xanthates: Selective Synthesis of α-Ketoesters and Esters

Cited by 15 publications

References 76 publications

Iodine and DMSO as Surrogate of Hazardous Metal and Non‐Metal Reagents in Organic Synthesis

Iodine and DMSO as Surrogate of Hazardous Metal and Non‐Metal Reagents in Organic Synthesis

Expedient Syntheses of Alkyl and Aryl Thioethers using Xanthates as Thiol-Free Reagents

The effect of experimental conditions on the formation of dixanthogen by triiodide oxidation in the determination of ethyl xanthate by HPLC–ICP-MS/MS

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