Interplay of Method Development and Mechanistic Studies – From Aerobic Oxidative Coupling to Radical Reactions via Alkenyl Peroxides

Klußmann, Martin; Schweitzer‐Chaput, Bertrand

doi:10.1055/s-0035-1560706

Cited by 4 publications

(2 citation statements)

References 14 publications

(36 reference statements)

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“…Xanthene structure widely exists in bioactive compounds, dyes, fluorescent materials, and so forth. − Various methodologies have been reported for the preparation of xanthene derivatives, particularly the synthesis of 9-substituted xanthene derivatives via oxidative CDC reaction between benzylic C(sp 3 )–H of xanthene and various active methylene compounds. − Transition-metal salts and peroxides are often used as close partners to activate carbon–hydrogen bonds for CDC reactions. Recently, Klussmann et al demonstrated that methane sulfonic acid was effective for the CDC reactions of xanthene and enolizable compounds with oxygen as the oxidant. − Elevated pressure of oxygen was required in the case of nucleophiles with poor reactivity . Additionally, notorious corrosion and potential environmental pollution restrict their practical applications.…”

Section: Introductionmentioning

confidence: 99%

Cooperative Interplay of Brønsted Acid and Lewis Acid Sites in MIL-101(Cr) for Cross-Dehydrogenative Coupling of C–H Bonds

Chen

Zhang

Chen

et al. 2021

ACS Appl. Mater. Interfaces

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Cross-dehydrogenative coupling (CDC) is an effective tool for carbon–carbon bond formation in chemical synthesis. Herein, we report a metal–organic framework (MOF) possessing dual Lewis acidic Cr sites and sulfonic acid sites (MIL-101(Cr)–SO3H) as an efficient catalytic material for direct cross-coupling of xanthene and different nucleophiles using O2 as the oxidant. The highly porous structure of MIL-101(Cr)–SO3H enables the free access of reactants to the catalytic active sites inside MOF pores. Kinetic studies indicated that the Cr sites of MOF accelerate the rate-limiting autoxidation reaction of xanthene, which synergistically work with the sulfonic acid group on MOF ligands in promoting the CDC reactions. Besides, the catalytic system shows excellent functional group compatibility, and a variety of valuable xanthene derivatives were synthesized with satisfactory yields. Furthermore, MIL-101(Cr)–SO3H can be reused and its catalytic activity and crystal structure remain after six consecutive runs.

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Section: Introductionmentioning

confidence: 99%

Cooperative Interplay of Brønsted Acid and Lewis Acid Sites in MIL-101(Cr) for Cross-Dehydrogenative Coupling of C–H Bonds

Chen

Zhang

Chen

et al. 2021

ACS Appl. Mater. Interfaces

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“…In a similar fashion, isoquinolinonediones 106 were synthesized from N ‐methacryloyl benzamides 105 (Scheme b) . The addition of a phenoxyl radical—derived from heteroaryl peroxide 22 (Scheme above)—to olefins was shown to work in a single case, although the product yield was rather low …”

Section: Solution Chemistrymentioning

confidence: 99%

Alkenyl and Aryl Peroxides

Klußmann

2017

Chemistry A European J

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Alkenyl and aryl peroxides are a special class of organic peroxides. Under ambient conditions, they are usually short-lived, rapidly decomposing into radicals by homolytic O-O bond cleavage. They play an important role in the chemistry of the lower atmosphere, where they are formed through ozonolysis of alkenes. In the dark, this pathway is considered the major source of hydroxyl radicals, the "detergent of the atmosphere". In solution, alkenyl and aryl peroxides can be formed by various methods and their decomposition can be harnessed synthetically. For example, reactions involving alkenyl peroxides can be used to introduce ketones through radical additions, and nucleophilic aromatic substitution reactions generating aryl peroxides have been used to synthesize phenols. The radicals can also initiate radical polymerization reactions or chain reactions and mediate oxidative coupling by C-H bond functionalization. Knowledge of their chemistry could be helpful for projects generating or utilizing peroxides.

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Oxidation and Reduction

Banerji¹

2020

Organic Reaction Mechanisms · 2016

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Interplay of Method Development and Mechanistic Studies – From Aerobic Oxidative Coupling to Radical Reactions via Alkenyl Peroxides

Cited by 4 publications

References 14 publications

Cooperative Interplay of Brønsted Acid and Lewis Acid Sites in MIL-101(Cr) for Cross-Dehydrogenative Coupling of C–H Bonds

Cooperative Interplay of Brønsted Acid and Lewis Acid Sites in MIL-101(Cr) for Cross-Dehydrogenative Coupling of C–H Bonds

Alkenyl and Aryl Peroxides

Oxidation and Reduction

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