Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls

Dubovtsev, Alexey Yu.; Shcherbakov, Nikolay V.; Dar’in, Dmitry; Kukushkin, Vadim Yu.

doi:10.1021/acs.joc.9b02785

Cited by 58 publications

(43 citation statements)

References 106 publications

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“…[35] Recently, the same group employed 2,3-dichloropyridine-Noxide 39 as the oxygen transfer reagent for the oxidation of alkynes 38 into 1,2-diketones 49 in the presence of 3 mol% of Au I catalyst Ph 3 PAuNTf 2 (Scheme 15). [36] Remarkably, this strategy is effective for a wide variety of alkynes 38 to obtain the corresponding 1,2-diketones 40 in good to excellent yields (56-99%). This protocol shows the application towards the one-pot synthesis of essential aza heterocyclic systems.…”

Section: Au-catalyzed Oxidationmentioning

confidence: 90%

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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Section: Au-catalyzed Oxidationmentioning

confidence: 90%

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

Kumar

Sridharan

2021

Asian J Org Chem

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“…[44] Dubovtsev, Kukushkin, and co-workers developed a gold(I)-catalyzed oxidation of alkynyl thioether 32 to α-ketomethylthioester 4 a in trifluorotoluene (PhCF 3 ) solvent in the presence of 2.5 equivalent 2,3-dichloropyridine N-oxide (33). [45] Due to the presence of 33 as an O-transfer reagent to alkynes, this process does not require any acid additives, which has been mostly used by others for similar transformations (Scheme 16).…”

Section: By Oxidationmentioning

confidence: 99%

“…[39][40][41][42] The oxidative thioesterification approach belongs to the most-studied synthetic methods till date. Among other methods, simple aerobic oxidation of α hydroxythioesters, [43][44] goldcatalyzed [45] and electrochemical oxidation [46] of alkynes have been used to access these valuable scaffolds (Section 2.4.). Dess-Martin periodinane (DMP)-initiated oxidative rearrangement of βhydroxythioesters [47] and BF 3 .OEt 2 -mediated tandem double cyclization of γ-alkylidenebutenolides [48] for accessing α-ketothioesters are also developed and are discussed in Section 2.5. α-Ketothioesters can also be accessed by radical-coupling approach, although it has been rarely explored.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in the Synthesis and Applications of α‐Ketothioesters

et al. 2021

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α‐Ketothioesters have only recently received widespread attention as synthetic intermediates and an impressive growth has been realized for their utilization in synthetic and medicinal chemistry. Several elegant approaches such as oxidative thioesterification and radical coupling allow for their convenient synthesis from easily available starting materials, e. g., methyl ketones, alkenes, alkynes, and α‐hydroxyketones. Due to their multifaceted and diverse reactivities, several important reactions such as C(O)−S bond cleavage and S‐migration with various C‐, N‐, and O‐based nucleophiles, Ni‐catalyzed mono‐ and double‐decarbonylations, enantioselective carbonyl‐ene reaction, diastereoselective hetero Diels‐Alder reactions with olefins, and different types of cyclization reactions have been observed. They have also proven to be a valuable tool for the synthesis of heterocycles, pharmaceutically relevant anticancer drug, and natural product. However, in comparison to other 1,2‐dicarbonyl derivatives such as α‐ketooxoesters, α‐ketoamides, and α‐ketoaldehydes, they are much less appreciated as synthetic intermediates. This review summarizes the recent advancements achieved in the synthesis of α‐ketothioesters as well as their applications in the development of new reactions for the formation of C−C, C−N, and C−O bonds, including multiple bond‐forming processes.

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“…Gold‐catalyzed conversion of gaseous acetylene generated in situ from calcium carbide to glyoxal 57 was carried out in a two‐chamber reactor (Figure 1A). [ 51 ] Quinoxaline 58 and triazine 59 were then directly synthesized from in situ generated glyoxal by heterocyclization (Scheme 22). Besides improved synthesis of substituted dicarbonyls new strategy for carbide utilization can be expanded under catalytic conditions.…”

Section: A Map Of Calcium Carbide Synthetic Transformationsmentioning

confidence: 99%

Calcium Carbide: Versatile Synthetic Applications, Green Methodology and Sustainability

et al. 2020

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Acetylene is a key building block for organic chemistry and potentially can be involved in a diverse range of synthetic transformations. However, critical analysis of practical considerations showed that application of gaseous acetylene in regular synthetic labs encounters a number of difficulties. Safety limitations due to flammable and explosive nature of gaseous acetylene and requirements for specialized high‐pressure equipment impose serious drawbacks. Typical reaction conditions involve excess of gaseous reactant, which is simply released to the atmosphere at the end of the reaction, thus generating waste and causing contamination. Calcium carbide brings a new green and sustainable wave into powerful alkyne transformations and significantly expands the repertoire of traditional acetylene chemistry. The novel trend of using calcium carbide instead of gaseous acetylene is synthetically beneficial and opens a novel reactivity for the C≡C unit. This review highlights recent advances in carbide chemistry, demonstrates its advantages and prospects in term of green synthetic approach.

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Nature of the Nucleophilic Oxygenation Reagent Is Key to Acid-Free Gold-Catalyzed Conversion of Terminal and Internal Alkynes to 1,2-Dicarbonyls

Cited by 58 publications

References 106 publications

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

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

Recent Advances in the Synthesis and Applications of α‐Ketothioesters

Calcium Carbide: Versatile Synthetic Applications, Green Methodology and Sustainability

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