Synthesis of unsymmetrical hetaryl-1,2-diketones

Yusubov, M. S.; Zholobova, G. A.; Vasilevsky, S. F.; Tretyakov, Evgeny V.; Knight, David W.

doi:10.1016/s0040-4020(02)00025-x

Cited by 45 publications

(24 citation statements)

References 12 publications

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“…Though all these transformations are suitable methods with a range of simple diarylalkynes, many of them display low chemoselectivity and provide low yields with substrates having sensitive functionalities. During the last decade, DMSO has been successfully used as an oxidant either in the presence of CH3SO3H/HCO2H/HBr 9 mixture or PdCl2 10 . Typically in the latter case, the reaction is reported to require high loading of catalyst (10 mol%) and long reaction times, sometimes extending into days that can seriously affect the yield and the outcome of the oxidation reaction, particularly with substrates having strong electronwithdrawing groups 5,11 (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…12 Additionally, the oxidation reaction is far from trivial with substrates containing a heteroaryl nucleus including for instance a pyridine or a pyrazole. 10,13 Therefore, alternative routes and more reliable procedures for the synthesis of benzils are welcome. The remaining challenge is to obtain highly substituted benzils from functionalized diarylalkynes without compromising reagent safety, simplicity and practicality.…”

Section: Introductionmentioning

confidence: 99%

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DMSO–PdI2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles

et al. 2008

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PdI2 in DMSO promoted the oxidation of functionalized diarylalkynes into benzil derivatives in excellent yields. This new oxidation reaction was achieved with short reaction times and low loading of palladium catalyst .This efficient catalytic process has been applied successfully to the one-pot construction of a series of nitrogen-containing heterocycles of biological interest according to a tandem oxidation-nitrogen nucleophiles condensation-cyclization.---*

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

DMSO–PdI2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles

et al. 2008

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“…15 While this transformation is a suitable method, its success was influenced by the electronic nature of the aryl-substituents. 16 A recent work concerning the oxidation of alkynes into -diketones with DMSO and CH3SO3H/ HCO2H/HBr 17 prompted us to report the results of our study. With respect to the environmental concerns, there is a strong demand for a clean, safe and highly efficient catalytic methodology for the conversion of aryl alkynes to benzil derivatives.…”

Section: Introductionmentioning

confidence: 93%

Microwave‐Assisted Efficient Synthesis of 1,2‐Diaryldiketones: A Novel Oxidation Reaction of Diarylalkynes with DMSO Promoted by FeBr₃.

et al. 2006

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“…Oxidation of substituted tolans by Wacker reaction is one of the most useful methods for the synthesis of 1,2‐diketones . Although several methods have been reported for the oxidation of alkynes, these reactions still suffer from drawbacks such as harsh conditions, narrow substrate scope and low yield and/or chemoselectivity …”

Section: Introductionmentioning

confidence: 99%

Practical and theoretical aspects of Wacker oxidation of tolanophanes: Synthesis and characterization of novel diketonic cyclophanes

Darabi

Rastgar

Khatamifar

et al. 2017

Applied Organom Chemis

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Novel cyclophanes having 1,2-diketones 2a-c were synthesized by Wacker oxidation of the corresponding tolanophanes 1a-c having various alkyl chain lengths (n = 2-4). Among them, tolanophane 1a with the shortest alkyl chain length (n = 2) having more strained alkyne shows the lowest product selectivity even lower than that of acyclic analogues at various reaction temperatures. In contrast, the oxidation of tolanophane 1b (n = 3) is clean with the highest activity and selectivity of 2b. Theoretical calculations confirm the experimental data. Based on ab initio calculations, the critical step of the reaction pathway is the interaction of oxygen atoms of 1 (in the absence of H 2 O) with Pd ion of intermediate [PdCl 3 (1)] − to give [PdCl 2 (1)] which keeps Pd ion close to the alkyne bond. This step is not observed computationally for 1a because the positions of the oxygen atoms are outside of its central part. This is in good agreement with almost no activity of 1a at room temperature to prove its rigid structure preventing the O…Pd interaction. Nevertheless, the alkyne…Pd interaction of 1b is not detected by NMR measurements which may be due to its too slow interaction at room temperature (35% after 24 h); however, this confirms ab initio calculation data that the preferred coordinating site is oxygen in the reaction pathway. In contrast, cyclic voltammetry measurements distinguish a different behaviour for the palladium complexation of 1. In general, it is found that the stereochemistry of tolanophanes rather than distortion of alkyne bond plays the critical role in the oxidation. The products are new and their structures were characterized.

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Synthesis of unsymmetrical hetaryl-1,2-diketones

Cited by 45 publications

References 12 publications

DMSO–PdI2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles

DMSO–PdI2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles

Microwave‐Assisted Efficient Synthesis of 1,2‐Diaryldiketones: A Novel Oxidation Reaction of Diarylalkynes with DMSO Promoted by FeBr₃.

Practical and theoretical aspects of Wacker oxidation of tolanophanes: Synthesis and characterization of novel diketonic cyclophanes

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Synthesis of unsymmetrical hetaryl-1,2-diketones

Cited by 45 publications

References 12 publications

DMSO–PdI2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles

DMSO–PdI2 as a powerful oxidizing couple of alkynes into benzils: one-pot synthesis of nitrogen-containing five- or six-membered heterocycles

Microwave‐Assisted Efficient Synthesis of 1,2‐Diaryldiketones: A Novel Oxidation Reaction of Diarylalkynes with DMSO Promoted by FeBr3.

Practical and theoretical aspects of Wacker oxidation of tolanophanes: Synthesis and characterization of novel diketonic cyclophanes

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Microwave‐Assisted Efficient Synthesis of 1,2‐Diaryldiketones: A Novel Oxidation Reaction of Diarylalkynes with DMSO Promoted by FeBr₃.