Chemoselective ester/ether C–O cleavage of methyl anisates by aluminum triiodide

Sang, Dayong; Yi, Cuicui; He, Zhoujun; Wang, Jiahui; Tian, Juan; Yao, Ming; Shi, Hong

doi:10.1016/j.tetlet.2018.03.010

Cited by 10 publications

(6 citation statements)

References 24 publications

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“…Cleavage of methyl 2‐anisate ( 4 m ) by AlCl 3 ‐NaI for 1 hour at room temperature afforded methyl salicylate 5 m in 68% yield. The demethylation of 4 m is envisioned to proceed via the coordination of the carboxylate oxygen to the Lewis acid followed by anchimeric effect facilitated ether cleavage . 3‐Methoxyphenol ( 4 n ) gave resorcinol ( 5 n ) in 35% yield under current conditions.…”

Section: Resultsmentioning

confidence: 99%

Anchimerically Assisted Cleavage of Aryl Methyl Ethers by Aluminum Chloride‐Sodium Iodide in Acetonitrile

Sang

Tian

et al. 2018

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A practical method is developed for the cleavage of catechol monomethyl ethers and o-carbonylphenyl methyl ethers using aluminum chloride and sodium iodide in acetonitrile. Acid scavengers such as 1,3-diisopropylcarbodiimide and CaO are used to prevent acid-labile functional groups from sidereactions. This method is efficient for the deprotection of various o-hydroxyphenyl methyl ethers such as acetovanillone, eugenol, guaiacol, vanillin, isovanillin and ortho-vanillin. The AlCl 3 -NaI system is less efficient than AlI 3 for the cleavage of other typical aryl alkyl ethers without a neighboring hydroxyl or carbonyl group, or for the removal of bulkier alkyl groups from catechol monoalkyl ethers. This procedure represents a convenient approach for the preparation of catechols. 2 3 4 5 6 7 8

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Section: Resultsmentioning

confidence: 99%

Anchimerically Assisted Cleavage of Aryl Methyl Ethers by Aluminum Chloride‐Sodium Iodide in Acetonitrile

Sang

Tian

et al. 2018

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“…Similarly, when methyl 2‐anisate ( 3x′ ) was exposed to the demethylation conditions, both the ether and ester C−O bonds were cleaved that afforded salicylic acid ( 4x′ ) in 90% yield (Table ). It should be noted that the deprotection efficiency is comparable to that using AlI 3 via the two‐stage process . Sterically hindered ethyl and isopropyl groups were also readily removed when catechol monoalkyl ethers 3 y and 3y′ were treated with the optimum conditions, giving catechol ( 4 j ) in 89% and 84% yield, respectively.…”

Section: Resultsmentioning

confidence: 94%

“…Since DMSO and DIC were used to scavenging HI for the protection of acid‐labile functional groups from side‐reactions, these additives were used only when needed. It should also be noted that heating is necessitated for the cleavage of typical aryl alkyl ethers by either aluminum oxide iodide or aluminum triiodide in the absence of neighboring group participation effect . Thus, the reactions were conducted in acetonitrile at 80 °C.…”

Section: Resultsmentioning

confidence: 96%

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

et al. 2019

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Cleavage of aryl alkyl ethers was conducted in a one-pot onestage manner by mixing the ethers, aluminum and iodine in acetonitrile without the in situ preparation of aluminum triiodide in advance. For ethers bearing acid-labile functional groups such as allyl, alkenyl and carbonyl, an acid scavenger (calcium oxide, 1,3-diisopropylcarbodiimide or dimethyl sulfoxide) was used to prevent side-reactions. This one-pot protocol is efficient and convenient for the removal of methyl, ethyl, isopropyl and tert-butyl groups from typical aryl alkyl ethers, catechol monomethyl and dimethyl ethers, and is compatible with a variety of functional groups including alkenyl, alkyl, allyl, amido, cyano, formyl, halogen, keto and nitro group. Methyl 2-anisate and eugenol acetate were exhaustively deprotected by the method that afforded salicylic acid and hydroxychavicol, respectively.

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“…We envisioned that N -benzylacylsulfonamides might react with AlCl 3 in a different manner based on a previous observation that although both AlCl 3 and AlI 3 are efficient in cleaving ether , and ester C–O bonds, these two Lewis acids display complementary reactivities toward aryl and alkyl carboxylic esters . The chloride favors deacylation, whereas the iodide prefers to attack the alkyl chemoselectively .…”

Section: Resultsmentioning

confidence: 99%

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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Chemoselective ester/ether C–O cleavage of methyl anisates by aluminum triiodide

Cited by 10 publications

References 24 publications

Anchimerically Assisted Cleavage of Aryl Methyl Ethers by Aluminum Chloride‐Sodium Iodide in Acetonitrile

Anchimerically Assisted Cleavage of Aryl Methyl Ethers by Aluminum Chloride‐Sodium Iodide in Acetonitrile

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

Chemoselective Cleavage of Acylsulfonamides and Sulfonamides by Aluminum Halides

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