One‐Pot Cleavage of Aryl Alkyl Ethers by Aluminum and Iodine in Acetonitrile

Tian, Juan; Yue, Huaxin; Yang, Pengtao; Sang, Dayong

doi:10.1002/slct.201803469

Cited by 15 publications

(8 citation statements)

References 19 publications

(17 reference statements)

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“…With these established methods, direct N-dealkylation and especially N-debenzylation of sulfonamides is still sometimes challenging. , Therefore, development of alternative methods for deprotecting sulfonamides remains favorable. We have recently effected ether and ester cleavages with AlI 3 , which is tolerant to a number of functional groups including aryl carboxylates, formyl, cyano, Boc, methoxymethyl, tetrahydropyranyl, tert -butyldimethylsilyl and allyl . We present herein that N -alkyl and N -acyl moieties of sulfonamides can be chemoselectively detached by AlI 3 and AlCl 3 , respectively (Scheme D).…”

Section: Introductionmentioning

confidence: 94%

Chemoselective Cleavage of Acylsulfonamides and Sulfonamides by Aluminum Halides

et al. 2022

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The chemoselective cleavage of C–N bonds of amides, sulfonamides, and acylsulfonamides by aluminum halides is described. AlCl3 and AlI3 display complementary reactivities toward N-alkyl and N-acyl moieties. N-Alkylacylsulfonamides, secondary N-(tert-butyl)sulfonamides, and tertiary N-(tert-butyl)amides undergo N-dealkylation upon treatments with AlI3 generated in situ from aluminum and iodine in acetonitrile. In contrast, AlCl3 preferentially cleaves N-acyl groups of tertiary and secondary sulfonamides.

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Section: Introductionmentioning

confidence: 94%

Chemoselective Cleavage of Acylsulfonamides and Sulfonamides by Aluminum Halides

et al. 2022

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“…For the reaction with DMSO, it is proposed that in situ formed aluminum oxide iodide is the reactive species [93] . A one‐pot method, comprised of mixing aryl alkyl ether substrates, aluminum powder, iodine, and an acid scavenger (if needed) in acetonitrile, without preparing aluminum triiodide beforehand, can also efficiently cleave the ether bonds of aryl alkyl ethers [95] . Furthermore, BF 3 −Me 2 S, [96] AlI 3 , and BCl 3 in combination with TBAI, [97] as well as the SiCl 4 −NaI couple were used for the demethylation of lignin‐derived monomers [98] .…”

Section: Odm Of Ortho‐methoxyphenolsmentioning

confidence: 99%

Advancements and Perspectives toward Lignin Valorization via O‐Demethylation

Wu,

Smet,

Brandi

et al. 2024

Angewandte Chemie

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Lignin represents the largest aromatic carbon resource in plants, holding significant promise as a renewable feedstock for bioaromatics and other cyclic hydrocarbons in the context of the circular bioeconomy. However, the methoxy groups of aryl methyl ethers, abundantly found in technical lignins and lignin‐derived chemicals, limit their pertinent chemical reactivity and broader applicability. Unlocking the phenolic hydroxyl functionality through O‐demethylation (ODM) has emerged as a valuable approach to mitigate this need and enables further applications. In this review, we provide a comprehensive summary of the progress in the valorization of technical lignin and lignin‐derived chemicals via ODM, both catalytic and non‐catalytic reactions. Furthermore, a detailed analysis of the properties and potential applications of the O‐demethylated products is presented, accompanied by a systematic overview of available ODM reactions. This review primarily focuses on enhancing the phenolic hydroxyl content in lignin‐derived species through ODM, showcasing its potential in the catalytic funneling of lignin and value‐added applications. A comprehensive synopsis and future outlook are included in the concluding section of this review.

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“…Besides the generation of halohydrocarbons, thioacidolysis is another acid-promoted method to cleave the ether bond R–O–R′ with Et 2 O·BF 3 and EtSH to offer a thioether and one R–OH (Figure A) . Furthermore, the reactions between ethers and acyl chlorides can provide the corresponding esters and halohydrocarbons catalyzed by various Lewis acid catalysts, such as ZnCl 2 , FeCl 3 , SnBr 2 , CoCl 2 , AlCl 3 , YCl 3 , LnCl 3 , and Al + I 2 , or other catalysts like Al, Zn, graphite, Mo(CO) 6 , and ArMo(CO) 3 . It is generally accepted that these catalytic reactions proceed via a cationic mechanism (Figure B).…”

Section: Cationic Intermediatesmentioning

confidence: 99%

Catalytic Strategies and Mechanism Analysis Orbiting the Center of Critical Intermediates in Lignin Depolymerization

et al. 2023

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Lignin, as a precious resource given to mankind by nature with abundant functional aromatic structures, has drawn much attention in the recent decade from academia to industry worldwide, aiming at harvesting aromatic compounds from this abundant and renewable natural polymer resource. How to efficiently depolymerize lignin to easy-to-handle aromatic monomers is the precondition of lignin utilization. Many strategies/methods have been developed to effectively degrade lignin into monomers, such as the traditional methods of pyrolysis, gasification, liquid-phase reforming, solvolysis, chemical oxidation, hydrogenation, reduction, acidolysis, alkaline hydrolysis, alcoholysis, as well as the newly developed redox-neutral process, biocatalysis, and combinatorial strategies. Therefore, there is a strong demand to systemically summarize these developed strategies and methods and reveal the internal transformation principles of the lignin. Focusing on the topic of lignin depolymerization to aromatic chemicals, this review reorganizes and categorizes the strategies/methods according to their mechanisms, orbiting the center of critical intermediates during the lignin linkage transformation, which includes the critical anionic intermediates, cationic intermediates, organometallic intermediates, organic molecular intermediates, aryl cation radical intermediates, and neutral radical intermediates. The corresponding introduction involves the generation and the transformation chemistry of the critical intermediates via the corresponding C–H/O–H/C–C/C–O chemical bond transformations, leading to the cleavage of the C–C/C–O linkage bonds. Accompanying the brief introduction of lignin chemistry and the final concluding remarks and perspectives on lignin depolymerization, this review aims to provide a current research process of lignin depolymerization, which may provide useful suggestions for this vigorous research field.

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One‐Pot Cleavage of Aryl Alkyl Ethers by Aluminum and Iodine in Acetonitrile

Cited by 15 publications

References 19 publications

Chemoselective Cleavage of Acylsulfonamides and Sulfonamides by Aluminum Halides

Chemoselective Cleavage of Acylsulfonamides and Sulfonamides by Aluminum Halides

Advancements and Perspectives toward Lignin Valorization via O‐Demethylation

Catalytic Strategies and Mechanism Analysis Orbiting the Center of Critical Intermediates in Lignin Depolymerization

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