Catalytic Deoxygenative Coupling of Aromatic Esters with Organophosphorus Compounds

Kurosawa, Miki B.; Isshiki, Ryota; Muto, Kei; Yamaguchi, Junichiro

doi:10.1021/jacs.0c02839

Cited by 29 publications

(20 citation statements)

References 87 publications

(45 reference statements)

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“…Yamaguchi reported a palladium-catalyzed deoxygenative coupling of aromatic esters (Scheme 26). 30 An electron-rich diphosphine (dcype) was used as a ligand, and sodium formate as a hydrogen source. The mechanism involves oxidative addition of the acyl C-O bond, ligand exchange from phenoxy, and reductive elimination.…”

Section: Scheme 25 Diverse Hirao Reactionsmentioning

confidence: 99%

Nucleophilic H-Phosphites, H-Phosphinates, and H-Phosphine Oxides in Organic Reactions

Wang¹,

Guo²,

Xu³

et al. 2021

Synthesis

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P(O)-H compounds like H-phosphites, H-phosphinates and H-phosphine oxides are widely used as nucleophiles. Herein, reactions with unsaturated compounds, C-H activation, Hiro reaction, P-C, P-S, P-O, P-N and P-F couplings were thoroughly discussed and summarized. This review will focus on their reactions with alkenes, alkynes, enamides, propiolic acids, epoxide, arynes, arenes, quinones, isothiocyanates, diazo compounds, aldehydes, ketones, imines, pyridines, acid derivatives, carbocations, aryl halides, dibromoalkenes, disulfides, thiosulfates, sulfonyl chlorides, iodonium salts, amines, alcohols and thioalcohols.

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Section: Scheme 25 Diverse Hirao Reactionsmentioning

confidence: 99%

Nucleophilic H-Phosphites, H-Phosphinates, and H-Phosphine Oxides in Organic Reactions

Wang¹,

Guo²,

Xu³

et al. 2021

Synthesis

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“…This compound is known. 18 (9H-Fluoren-9-yl)diphenylphosphine Oxide (3s). The title compound was prepared according to the general experimental procedure I, purified by column chromatography on silica gel, and eluted with DCM:EA = 5:1 (v/v) to afford a white solid in 44% yield (32.2 mg).…”

Section: Scheme 2 Investigation Of the Counterion Effectmentioning

confidence: 99%

Transition-Metal-Free and Base-Promoted Carbon–Heteroatom Bond Formation via C–N Cleavage of Benzyl Ammonium Salts

et al. 2021

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A facile and general method for constructing carbon–heteroatom (C–P, C–O, C–S, and C–N) bonds via C–N cleavage of benzyl ammonium salts under transition-metal-free conditions was reported. The combination of t-BuOK and 18-crown-6 enabled a wide range of substituted benzyl ammonium salts to couple readily with different kinds of heteroatom nucleophiles, i.e. hydrogen phosphoryl compounds, alcohols, thiols, and amines. Good functional group tolerance was demonstrated. The scale-up reaction and one-pot synthesis were also successfully performed.

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“…Consecutive removals of C–O bonds through boron group transfer could give a gem -diboron intermediate, which was susceptible for protodeboronation to furnish the final product. Interestingly, similar acyl species have been proposed as intermediacy for carboxylic acid deoxygenative phosphorylation and carbon monoxide reduction 25 – 28 .…”

Section: Resultsmentioning

confidence: 85%

Direct deoxygenative borylation of carboxylic acids

Huang

Ataya

et al. 2021

Nat Commun

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Carboxylic acids are readily available, structurally diverse and shelf-stable; therefore, converting them to the isoelectronic boronic acids, which play pivotal roles in different settings, would be highly enabling. In contrast to the well-recognised decarboxylative borylation, the chemical space of carboxylic-to-boronic acid transformation via deoxygenation remains underexplored due to the thermodynamic and kinetic inertness of carboxylic C-O bonds. Herein, we report a deoxygenative borylation reaction of free carboxylic acids or their sodium salts to synthesise alkylboronates under metal-free conditions. Promoted by a uniquely Lewis acidic and strongly reducing diboron reagent, bis(catecholato)diboron (B2cat2), a library of aromatic carboxylic acids are converted to the benzylboronates. By leveraging the same borylative manifold, a facile triboration process with aliphatic carboxylic acids is also realised, diversifying the pool of available 1,1,2-alkyl(trisboronates) that were otherwise difficult to access. Detailed mechanistic studies reveal a stepwise C-O cleavage profile, which could inspire and encourage future endeavours on more appealing reductive functionalisation of oxygenated feedstocks.

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Catalytic Deoxygenative Coupling of Aromatic Esters with Organophosphorus Compounds

Cited by 29 publications

References 87 publications

Nucleophilic H-Phosphites, H-Phosphinates, and H-Phosphine Oxides in Organic Reactions

Nucleophilic H-Phosphites, H-Phosphinates, and H-Phosphine Oxides in Organic Reactions

Transition-Metal-Free and Base-Promoted Carbon–Heteroatom Bond Formation via C–N Cleavage of Benzyl Ammonium Salts

Direct deoxygenative borylation of carboxylic acids

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