Nickel-catalyzed 1,4-aryl rearrangement of aryl <i>N</i>-benzylimidates <i>via</i> C–O and C–H bond cleavage

Ogawa, Satoshi; Tobisu, Mamoru

doi:10.1039/d2cc02355e

Cited by 3 publications

(2 citation statements)

References 25 publications

(7 reference statements)

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“…[2,3] Recently, a Ni-catalyzed rearrangement was developed for the transformation of N-benzyl imidates 211 to the desired products 212 via a [1,4]-aryl migration. [88] This method combined Ni(cod) 2 as the most appropriate catalyst and 1,2-bis(dicyclohexylphosphino)ethane (dcpe) as the ligand, at 160 °C. A series of aryl-substituted imidates were tested and the corresponding products 212 were formed in moderate to good yields (Scheme 54).…”

Section: Miscellaneous Applications Of Imidatesmentioning

confidence: 99%

“…As mentioned above, the aryl N ‐benzimidates have the capacity to rearrange via an 1,3‐aryl shift (Chapman rearrangement) and transform into amides [2,3] . Recently, a Ni‐catalyzed rearrangement was developed for the transformation of N ‐benzyl imidates 211 to the desired products 212 via a [1,4]‐aryl migration [88] . This method combined Ni(cod) 2 as the most appropriate catalyst and 1,2‐bis(dicyclohexylphosphino)ethane (dcpe) as the ligand, at 160 °C.…”

Section: Diverse Applications Of Imidatesmentioning

confidence: 99%

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Synthetic Routes to Imidates and Their Applications in Organic Transformation: Recent Progress

Chaidali,

Lykakis

2023

Eur J Org Chem

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Recent synthetic approaches and diverse applications of imidates are presented in this review. These motifs are successfully used as intermediates in organic transformations, such as the synthesis of N‐heterocycles, natural products and metal complexes with a potential catalytic effect. Consequently, many attempts have been made for the development of efficient and facile synthetic methods of imidates in the past few years, as a continuum of previous paths. A wide range of organic compounds can be used as starting materials for these syntheses, including nitriles, isocyanides, amides etc. which through simple and flexible processes are converted to the desired imidates. Herein, an exploration of the recent synthetic routes of imidates and their diverse applications in organic transformations has been categorized and summarized.

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Section: Miscellaneous Applications Of Imidatesmentioning

confidence: 99%

Section: Diverse Applications Of Imidatesmentioning

confidence: 99%

Synthetic Routes to Imidates and Their Applications in Organic Transformation: Recent Progress

Chaidali,

Lykakis

2023

Eur J Org Chem

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Transition Metal‐FreeO‐Arylation ofN‐Alkoxybenzamides Enabled by Aryl(trimethoxyphenyl)iodonium Salts

et al. 2023

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Herein, we develop a metal catalyst‐free protocol for O‐arylation of benzamide hydroxamate esters. The chemoselective O‐ versus N‐arylation of the amides was tuned by varying the electronic and/or steric properties of the diaryliodonium salt and/or the substrate. The O‐arylation reaction would preferentially occur for sterically and electronically diverse substrates. This study, which reveals the possibility of substituent‐ and reagent‐controlled chemoselectivity, with diaryliodonium salts might attract interest in the area of hypervalent iodine chemistry.magnified image

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Merging Pd(0)-Catalyzed Selective C_acyl–O Bond Activation of Enol Esters with π-Acid Catalysis: Net Hydroxyacylation of Aliphatic Alkynes with Carboxylic Acids

Michigami,

Otawa,

Kanda

et al. 2024

ACS Catal.

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A catalytic system comprising Pd(0) and N-heterocyclic carbene (NHC) demonstrated remarkable efficiency in the acyl migration of enol carboxylates via the regioselective cleavage of the C acyl −O bond. Employing NHC ligands with appropriate steric bulkiness and electrondonating ability enabled the transformation of a diverse array of enol esters containing alkyl-substituted internal and terminal alkenes into unsymmetrical β-diketones. Merging this methodology with π-acidcatalyzed hydroacyloxylation of alkynes delivered a formal catalytic alkyne insertion into the C acyl −O bond of carboxylic acid. In addition to the essential roles of both Pd and NHC in driving the reaction, the intramolecular aspects were also unveiled through a crossover experiment. Elucidation of mechanistic insights via DFT studies suggested the kinetic preference for oxidative addition of the C acyl −O bond over the C enol −O and the C acyl −C aryl bonds, aligning well with perfect selectivity in the experiments. Tentatively, reductive elimination of the C−C bond occurs directly from the acylpalladium oxa-π-allyl complex without intermediacy of acylpalladium C-enolate.

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Nickel-catalyzed 1,4-aryl rearrangement of aryl N-benzylimidates via C–O and C–H bond cleavage

Abstract: We report herein that nickel-catalyzed reaction of aryl imidates bearing an N-benzyl group results in 1,4-migration of an O-aryl group via the cleavage of C–O and C–H bonds. This protocol...

Cited by 3 publications

References 25 publications

Synthetic Routes to Imidates and Their Applications in Organic Transformation: Recent Progress

Synthetic Routes to Imidates and Their Applications in Organic Transformation: Recent Progress

Transition Metal‐FreeO‐Arylation ofN‐Alkoxybenzamides Enabled by Aryl(trimethoxyphenyl)iodonium Salts

Merging Pd(0)-Catalyzed Selective C_acyl–O Bond Activation of Enol Esters with π-Acid Catalysis: Net Hydroxyacylation of Aliphatic Alkynes with Carboxylic Acids

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Nickel-catalyzed 1,4-aryl rearrangement of aryl N-benzylimidates via C–O and C–H bond cleavage

Abstract: We report herein that nickel-catalyzed reaction of aryl imidates bearing an N-benzyl group results in 1,4-migration of an O-aryl group via the cleavage of C–O and C–H bonds. This protocol...

Cited by 3 publications

References 25 publications

Synthetic Routes to Imidates and Their Applications in Organic Transformation: Recent Progress

Synthetic Routes to Imidates and Their Applications in Organic Transformation: Recent Progress

Transition Metal‐FreeO‐Arylation ofN‐Alkoxybenzamides Enabled by Aryl(trimethoxyphenyl)iodonium Salts

Merging Pd(0)-Catalyzed Selective Cacyl–O Bond Activation of Enol Esters with π-Acid Catalysis: Net Hydroxyacylation of Aliphatic Alkynes with Carboxylic Acids

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Merging Pd(0)-Catalyzed Selective C_acyl–O Bond Activation of Enol Esters with π-Acid Catalysis: Net Hydroxyacylation of Aliphatic Alkynes with Carboxylic Acids