Palladium-Catalyzed Denitrative Synthesis of Aryl Nitriles from Nitroarenes and Organocyanides

Iizumi, Keiichiro; Tanaka, Hiroki; Muto, Kei; Yamaguchi, Junichiro

doi:10.1021/acs.orglett.4c01118

Cited by 6 publications

(2 citation statements)

References 74 publications

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“…In fact, reactions with metal cyanide reagents hardly proceed. It is known that metal reagents can be deactivated by an excess of cyanide, and this reagent could be effective with inactive aromatic electrophiles like aromatic esters, which undergo oxidative addition more slowly than haloarenes . Moreover, cinnamic acid derivatives were applicable, as well.…”

Section: Decarbonylative Couplingmentioning

confidence: 99%

“…It is known that metal reagents can be deactivated by an excess of cyanide, 38 and this reagent could be effective with inactive aromatic electrophiles like aromatic esters, which undergo oxidative addition more slowly than haloarenes. 39 Moreover, cinnamic acid derivatives were applicable, as well. The utility of this reaction was demonstrated by cyanation of a pharmaceutical scaffold derived from a probenecid.…”

Section: Decarbonylative Couplingmentioning

confidence: 99%

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Divergent Transformations of Aromatic Esters: Decarbonylative Coupling, Ester Dance, Aryl Exchange, and Deoxygenative Coupling

Kubo,

Yamaguchi

2024

Acc. Chem. Res.

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Conspectus Aromatic esters are cost-effective, versatile, and commonly used scaffolds that are readily synthesized or encountered as synthetic intermediates. While most conventional reactions involving these esters are nucleophilic acyl substitutions or 1,2-nucleophilic additionswhere a nucleophile attacks the carbonyl group, decarbonylative transformations offer an alternative pathway by using the carbonyl group as a leaving group. This transition-metal-catalyzed process typically begins with oxidative addition of the C(acyl)–O bond to the metal. Subsequently, the reaction involves the migration of CO to the metal center, the reaction with a nucleophile, and reductive elimination to yield the final product. Pioneering work by Yamamoto on nickel complexes and the development of decarbonylative reactions (such as Mizoroki–Heck-type olefination) using aromatic carboxylic anhydrides catalyzed by palladium were conducted by de Vries and Stephan. Furthermore, reports have surfaced of decarbonylative hydrogenation of pyridyl methyl esters by Murai using ruthenium catalysts as well as Mizoroki–Heck-type reactions of nitro phenyl esters by Gooßen under palladium catalysis. Our group has been at the forefront of developing decarbonylative C–H arylations of phenyl esters with 1,3-azoles and aryl boronic acids using nickel catalysts. The key to this reaction is the use of phenyl esters, which are easy to synthesize, stabilize, and handle, allowing oxidative addition of the C(acyl)–O bond; nickel, which facilitates oxidative addition of the C(acyl)–O bond; and suitable bidentate phosphine ligands that can stabilize the intermediate. By modification of the nucleophiles, esters have been effectively utilized as electrophiles in cross-coupling reactions, encouraging the development of these nucleophiles among researchers. This Account summarizes our advancements in nucleophile development for decarbonylative coupling reactions, particularly highlighting the utilization of aromatic esters in diverse reactions such as alkenylation, intramolecular etherification, α-arylation of ketones, C–H arylation, methylation, and intramolecular C–H arylation for dibenzofuran synthesis, along with cyanation and reductive coupling. We also delve into reaction types that are distinct from typical decarbonylative reactions, including ester dance reactions, aromatic ring exchanges, and deoxygenative transformations, by focusing on the oxidative addition of the C(acyl)–O bond of the aromatic esters to the metal complex. For example, the ester dance reaction is hypothesized to undergo 1,2-translocation starting with oxidative addition to a palladium complex, leading to a sequence of ortho-deprotonation/decarbonylation, followed by protonation, carbonylation, and reductive elimination. The aromatic exchange reaction likely involves oxidative addition of complexes of different aryl electrophiles with a nickel complex. In deoxygenative coupling, an oxidative addition complex with palladium engages with a nucleophile, forming an acyl intermediate that ...

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Section: Decarbonylative Couplingmentioning

confidence: 99%

Section: Decarbonylative Couplingmentioning

confidence: 99%

Divergent Transformations of Aromatic Esters: Decarbonylative Coupling, Ester Dance, Aryl Exchange, and Deoxygenative Coupling

Kubo,

Yamaguchi

2024

Acc. Chem. Res.

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Denitrative Functionalization of Nitroarenes: Recent Progress and Future Perspectives

Li,

Lei,

Yang

et al. 2024

Eur J Org Chem

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Nitroarenes are fundamental feedstocks in the chemical industry. Their relatively inert C−NO2 bond allows for late‐stage modifications of molecules and exhibits complete orthogonality to the reactivity of C−halogen bond in cross‐coupling reactions. The denitrative functionalization of nitroarenes holds significant appeal due to it avoids the use of aryl halides, thereby simplifying reaction steps and improving atom and step economy. Recent progress in direct denitrative functionalization of nitroarenes includes palladium‐catalyzed denitrative coupling, copper‐catalyzed denitrative coupling, as well as metal‐free one‐pot C−NO2 functionalization. In this review, we provide a concise overview of these advancements, detailing the reaction features and mechanisms. This summary aims to highlight the versatility and efficiency of denitrative functionalization methodologies, offering insights into their potential applications and inspiring further research in this promising area of organic synthesis.

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Oxidative Addition of Nitro-Perylenediimide onto Palladium(0): A Theoretical and Experimental Study

Schleinitz,

Chinchilla-Garzon,

Perfetto

et al. 2024

Organometallics

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Palladium-Catalyzed Denitrative Synthesis of Aryl Nitriles from Nitroarenes and Organocyanides

Cited by 6 publications

References 74 publications

Divergent Transformations of Aromatic Esters: Decarbonylative Coupling, Ester Dance, Aryl Exchange, and Deoxygenative Coupling

Divergent Transformations of Aromatic Esters: Decarbonylative Coupling, Ester Dance, Aryl Exchange, and Deoxygenative Coupling

Denitrative Functionalization of Nitroarenes: Recent Progress and Future Perspectives

Oxidative Addition of Nitro-Perylenediimide onto Palladium(0): A Theoretical and Experimental Study

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