Copper/Iodine‐Cocatalyzed C‐C Cleavage of 1,3‐Dicarbonyl Compounds Toward 1,2‐Dicarbonyl Compounds

Chen, Li‐Sha; Zhang, Lu‐Bing; Tian, Yajie; Li, Jin‐Heng; Liu, Yong‐Quan

doi:10.1002/ejoc.202000795

Cited by 13 publications

(8 citation statements)

References 65 publications

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“…The decomposition of C was supposed to occur spontaneously, furnishing the key trione intermediate D along with an oxo complex E . The coordination of D with E might trigger a 1,2-Wagner–Meerwein-type rearrangement , to yield a benzoyl oxide intermediate F , which could convert to 3b by releasing a complex G containing a CO ligand. The extrusion of a CO 2 molecule from G allowed for the regeneration of the initial catalyst .…”

Section: Resultsmentioning

confidence: 99%

“…The synthesis of benzils and related 1,2-dicarbonyl products is an ongoing endeavor for the synthetic community. As such, a great number of methods have been developed − with the majority of them focusing on the oxidation of various aromatic substrates. − These oxidative strategies can be generally classified as: (a) oxidation of ketones, α-halo-, and α-hydroxylketones, (b) oxidative addition of stilbenes, (c) oxidative addition of diaryl alkynes, (d) oxidation of 1,2-diarylethanes and hydrobenzoins, and (e) oxidative cleavage of α,β-unsaturated ketones or 1,3-diones via a metal-assisted decarbonylation of triketone intermediates (Scheme ). Despite the abundant literature, the pursuit of new methodologies is still considered to be meaningful, especially for those involving mild, simple, and less toxic oxidant systems.…”

Section: Introductionmentioning

confidence: 99%

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Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils

Zhu

Tsai

2020

J. Org. Chem.

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The conversion of 1,3-diaryl-2-diazo-1,3-diketones to 1,2-daryl-1,2-diketones (benzils) is reported based on a rhodium(II)-catalyzed aerobic decomposition process. The reaction occurs at ambient temperatures and can be catalyzed by a few dirhodium carboxylates (5 mol %) under a balloon pressure of oxygen. Moreover, an oxygen atom from the O 2 reagent is shown to be incorporated into the product, and this is accompanied by the extrusion of a carbonyl unit from the starting materials. Mechanistically, it is proposed that the decomposition may proceed via the interaction of a ketene intermediate resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical species generated upon the activation of molecular oxygen. The proposed mechanism has been supported by the results from a set of controlled experiments. By using this newly developed strategy, a large array of benzil derivatives as well as 9,10-phenanthrenequinone were synthesized from the corresponding diazo substrates in varying yields. On the other hand, the method did not allow the generation of benzocyclobutene-1,2-dione from 2-diazo-1,3-indandione because of the difficulty of inducing the initial rearrangement.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils

Zhu

Tsai

2020

J. Org. Chem.

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“…After the use of single catalyst in an routine oxidative degradation of 1,3‐diaryldiketones, cocatalyst were explored for the synthesis of benzils derivatives by Chen and co‐workers [127] . Copper/Iodine‐cocatalyzed C−C Cleavage of 1,3‐diaryldiketones 40 and the protocol was performed efficiently in DMSO as an oxidant at elevated temperatures to higher yields of benzils 48 (Scheme 25).…”

Section: Methods Of Synthesis Of Benzilsmentioning

confidence: 99%

Benzils: A Review on their Synthesis

2022

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This review segregates and outlines all the aspects of the synthesis of Benzil for almost two centuries. Here, state of the art review includes the early synthesis in 1836 to the advancement made over the past years in the knowledge of the preparation of benzil derivatives till the present. Benzil is one of the important and highly underrated organic compounds in which two adjacent carbonyl groups are flanked by two phenyl rings. Apart from its diverse functionality, the reactivity of benzils proclaims its prospects as a reagent for the synthesis of various heterocycles. On recasting benzil, it is possible to obtain a wide variety of utilities in pharmaceuticals, polymer, and material chemistry. This contemplation of the review gives a general perspective of reaction routes, mechanisms and highlights the conversions due to oxidation, and accentuates benzil as an emerging putative target.

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“…Very recently, copper and iodine-catalyzed reaction of 1,3dicarbonyl compounds 95 to access the corresponding 1,2dicarbonyl compounds 96 was reported by Chen, Li, Liu, and co-workers (Scheme 36). [60] In this approach, DMSO plays dual role as solvent and as the oxidant. A wide range of 1,2dicarbonyl compounds, namely, 1,2-diketones, 1,2-ketoamides, and 1,2-ketoesters were synthesized under the optimized conditions in good to excellent yields.…”

Section: Starting From 13-dicarbonyl Compoundsmentioning

confidence: 99%

Transition Metal‐Catalyzed Synthesis of 1,2‐Diketones: An Overview

Kumar

Sridharan

2021

Asian J Org Chem

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The 1,2-diketone structural motif is present in various natural products and compounds of biological significance. In addition, these compounds are frequently used as precursors or intermediates in several synthetically important organic transformations. The transition-metal catalysis plays an essential role for the generation of several carbon-carbon and carbon-heteroatom bonds to access diverse heterocyclic compounds. This metal-catalyzed approach has been frequently used for the synthesis of these valuable 1,2-diketones. This review summarizes the various approaches involving the transition metal-catalyzed synthesis of 1,2-diketones from easily accessible staring materials.

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Copper/Iodine‐Cocatalyzed C‐C Cleavage of 1,3‐Dicarbonyl Compounds Toward 1,2‐Dicarbonyl Compounds

Cited by 13 publications

References 65 publications

Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils

Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils

Benzils: A Review on their Synthesis

Transition Metal‐Catalyzed Synthesis of 1,2‐Diketones: An Overview

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