Synergistic Effect of Ketone and Hydroperoxide in Brønsted Acid Catalyzed Oxidative Coupling Reactions

Schweitzer‐Chaput, Bertrand; Sud, Abhishek; Pintér, Ákos; Dehn, Stefanie; Schulze, Philipp; Klußmann, Martin

doi:10.1002/anie.201306752

Cited by 98 publications

(46 citation statements)

References 65 publications

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“…Then, two possible pathways might be involved in the process: in pathway A, intermediate IV undergoes reduction to form intermediate V along with diphenyl disulfide. Alternatively, in pathway B, intermediate V and H 2 O 2 are generated by a substitution reaction between H 2 O and IV (H 2 O 2 was detected by UV/Vis spectroscopy; see the Supporting Information for details) . Finally, the target molecule 3 b and a molecule of HOP(O)(OEt) 2 are produced by means of intramolecular nucleophilic substitution…”

Section: Methodsmentioning

confidence: 99%

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Catalyst‐Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β‐Keto Sulfides and Sulfones

Wang

et al. 2016

Chemistry A European J

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Difunctionalization of activated alkenes, a powerful strategy in chemical synthesis, has been accomplished for direct synthesis of a series of β-keto sulfides and β-keto sulfones. The transformation, mediated by O2 , proceeds smoothly in water and without any catalyst. Prominent advantages of this method include mild reaction conditions, purification simplicity, and gram-scale synthesis, underlining the practical utility of this methodology.

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Section: Methodsmentioning

confidence: 99%

“…Alternatively, in pathway B, intermediate V and H 2 O 2 are generated by as ubstitution reaction between H 2 Oa nd IV (H 2 O 2 was detectedb yU V/Vis spectroscopy;s ee the Supporting Information for details). [11] Finally,t he target molecule 3b and am olecule of HOP(O)(OEt) 2 are produced by means of intramolecular nucleophilic substitution.…”

mentioning

confidence: 99%

Catalyst‐Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β‐Keto Sulfides and Sulfones

Wang

et al. 2016

Chemistry A European J

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“…In one report, oxidative coupling reactions were most likely mediated by radicals formed from alkenyl peroxides, although the reaction was not investigated in great detail and this mechanism was not suggested. Substrates bearing activated benzylic methylene groups, for example, xanthene ( 107 ), underwent an oxidative coupling reaction with C‐nucleophiles in the presence of ketones and t BuOOH as well as catalytic amounts of methane sulfonic acid (Scheme ) …”

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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“…Simply stirring the substrates under oxygen in the presence of an acid catalyst leads to the formation of the new products. Key to the reaction is the facile formation of intermediate hydroperoxides, which are substituted with the second substrate by acid catalysis 15 . The reaction, however, is restricted to xanthene and a few related compounds that are easily oxidized under an atmosphere of oxygen and the products have so far not found applications.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

Gulzar

Klußmann

2014

JoVE

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The direct functionalization of C-H bonds is an important and long standing goal in organic chemistry. Such transformations can be very powerful in order to streamline synthesis by saving steps, time and material compared to conventional methods that require the introduction and removal of activating or directing groups. Therefore, the functionalization of C-H bonds is also attractive for green chemistry. Under oxidative conditions, two C-H bonds or one C-H and one heteroatom-H bond can be transformed to C-C and C-heteroatom bonds, respectively. Often these oxidative coupling reactions require synthetic oxidants, expensive catalysts or high temperatures. Here, we describe a two-step procedure to functionalize indole derivatives, more specifically tetrahydrocarbazoles, by C-H amination using only elemental oxygen as oxidant. The reaction uses the principle of C-H functionalization via Intermediate PeroxideS (CHIPS). In the first step, a hydroperoxide is generated oxidatively using visible light, a photosensitizer and elemental oxygen. In the second step, the N-nucleophile, an aniline, is introduced by Brønsted-acid catalyzed activation of the hydroperoxide leaving group. The products of the first and second step often precipitate and can be conveniently filtered off. The synthesis of a biologically active compound is shown

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Synergistic Effect of Ketone and Hydroperoxide in Brønsted Acid Catalyzed Oxidative Coupling Reactions

Cited by 98 publications

References 65 publications

Catalyst‐Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β‐Keto Sulfides and Sulfones

Catalyst‐Free Difunctionalization of Activated Alkenes in Water: Efficient Synthesis of β‐Keto Sulfides and Sulfones

Alkenyl and Aryl Peroxides

Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides (CHIPS)

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