Metal-free site selective cross-coupling of pyridines with secondary phosphine chalcogenides using acylacetylenes as oxidants

Трофимов, Б. А.; Volkov, Pavel А.; Khrapova, Kseniya O.; Telezhkin, Anton A.; Иванова, Н. И.; Albanov, A. I.; Гусарова, Н. К.; Чупахин, О. Н.

doi:10.1039/c8cc01155a

Cited by 29 publications

(34 citation statements)

References 24 publications

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“…In 2018, Trofimov and co‐workers found that pyridines easily underwent site‐selective cross‐coupling with secondary phosphine chalcogenides in the presence of acylphenylacetylenes under mild conditions to give 4‐chalcogenophosphorylated pyridines in up to 71% yield . The acylphenylacetylenes acted as oxidants, being reduced to the corresponding E ‐configured olefins in this new type of S N H Ar reaction.…”

Section: Direct Phosphorylation Of the Parent Heterocyclesmentioning

confidence: 99%

Recent Advances in the Construction of Phosphorus‐Substituted Heterocycles, 2009–2019

2020

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Scheme 20. Phosphonation of pyridinones.Scheme 21. CuI-catalyzed phosphoramidate formation.Scheme22. Phosphonation of coumarin and quinolinone.Scheme23. Silver(I)-catalyzed phosphonation of coumarins. Scheme 33. Electrochemical C(sp 2 )ÀHphosphonation of quinoxaline-2(1H)-ones. Scheme 39. Phosphorylation of quinoxaline-2(1 H)-ones. Scheme40. Autoxidative phosphorylation of quinoxalines. Scheme 41. DTBP-mediated formation of phosphonated benzothiazoles. Scheme42. Phosphonation of imidazole[2,1-b]thiazoles.Scheme 47. Copper(I)-catalyzedp hosphonationo fN-iminoisoquinolinium ylides. Scheme48. Aerobic phosphonationofC ( sp 3 ) À Hbonds. Scheme 49. Copper(II)/PBQ-catalyzed phosphorylation of 3,4-dihydro-1,4-benzoxazin-2-ones. Scheme 87. Asymmetric exo-selective [3+ +2] cycloaddition to afford phosphorus-substituted pyrrolidines. Scheme 95. Cascade condensation/cyclization to phosphonylated thienopyridines. Scheme 96. S N Ar'-involved cascade reactions to phosphonylated oxygenorn itrogen heterocycles.Scheme 97. Manganese(III)-mediated synthesis of 3-phosphonyldihydrofuransfrom b-ketophosphonates.Scheme98. Cyclization to phosphonated isochromenes.Scheme 121. Asymmetric [4+ +2] cycloaddition of b,g-unsaturated a-ketophosphonates.

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Section: Direct Phosphorylation Of the Parent Heterocyclesmentioning

confidence: 99%

Recent Advances in the Construction of Phosphorus‐Substituted Heterocycles, 2009–2019

2020

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“…In 2018, it was found that the regioselective oxidative cross-coupling reaction between pyridines 1a,b and secondary phosphine chalcogenides 2a-j was triggered and further driven by electrophilic acetylenes 3a-d to produce S N H products, phosphorylated pyridines 4a-n, and E-acylphenylethenes 5a-d (Scheme 1) [37]. The reaction tolerates a quite representative number of structurally diverse secondary phosphine chalcogenides (oxides, sulfides and selenides), having both aromatic and alkyl aromatic substituents.…”

Section: One-step S N H Phosphorylationmentioning

confidence: 99%

“…The reaction tolerates a quite representative number of structurally diverse secondary phosphine chalcogenides (oxides, sulfides and selenides), having both aromatic and alkyl aromatic substituents. The reaction involves the reversible generation of 1,3-dipole A via a nucleophilic attack of pyridine nitrogen at the electron-deficient triple bond (Scheme 2) [37].…”

Section: One-step S N H Phosphorylationmentioning

confidence: 99%

“…The mechanism is supported by the detection of the intermediate dihydropyridine 7a in a mixture ( 1 H and 31 P NMR) with the corresponding pyridine 4i, when pyridine 1a reacts (room temperature, MeCN, 4 h) with terminal furoylacetylene 6a (having no phenyl substituent in position two) and phosphine selenide 2i (Scheme 3). The perdeuteropyridine (pyridine-d 5 ) with phosphine sulfide 2f and acetylene 3c afforded the isotopically labeled cross-coupling product, 4-[bis(2-phenylethyl)thiophosphoryl] pyridine-d 4 , in a 42% yield (for 50 h) [37]. The low yield and longer reaction time compared to those for non-deuterated pyridine (71%, 35 h) are likely due to the deuterium kinetic isotopic effect.…”

Section: One-step S N H Phosphorylationmentioning

confidence: 99%

“…A short time ago [37][38][39][40], the nucleophilic substitution of hydrogen (S N H reaction) in non-activated pyridines and their fused derivatives by secondary phosphine chalcogenides (synthesized from red phosphorus [41][42][43][44]) in the presence of electron-deficient terminal and internal acetylenes was disclosed. These reactions involve the step of N-vinylation/ C-phosphorylation of pyridinoids, and are often retained at this step [45][46][47][48][49].…”

Section: Introductionmentioning

confidence: 99%

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Electron-Deficient Acetylenes as Three-Modal Adjuvants in SNH Reaction of Pyridinoids with Phosphorus Nucleophiles

2021

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Publications covering a new easy metal-free functionalization of pyridinoids (pyridines, quinolines, isoquinolines, acridine) under the action of the system of electron-deficient acetylenes (acetylenecarboxylic acid esters, acylacetylenes)/P-nucleophiles (phosphine chalcogenides, H-phosphonates) are reviewed. Special attention is focused on a SNH reaction of the regioselective cross-coupling of pyridines with secondary phosphine chalcogenides triggered by acylacetylenes to give 4-chalcogenophosphorylpyridines. In these processes, acetylenes act as three-modal adjuvants (i) activating the pyridine ring towards P-nucleophiles, (ii) deprotonating the P-H bond and (iii) facilitating the nucleophilic addition of the P-centered anion to a heterocyclic moiety followed by the release of the selectively reduced acetylenes (E-alkenes).

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Chichibabin‐Type Phosphonylation of 2‐(Hetero)aryl Pyridines: Selective Synthesis of 4‐Phosphinoyl Pyridines via an Activated N‐Benzylpyridinium Salt

et al. 2022

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A direct C−H phosphonylation of pyridine by N‐benzylating activation is reported, which afforded 4‐pyridylphosphine oxides with high regioselectivity, without the employment of metal catalyst or expensive activator. By increasing the electrophilicity of pyridinium with electron‐withdrawing substituents on the N‐benzyl group, the phosphonylation process could be realized at room temperature. Control experiments and NMR investigation confirmed the interaction between DBU and diphenylphosphine oxide which generated the true phosphorus nucleophile. Moreover, DFT calculations offered enough insight into an intermolecular cooperative dehydrogenation‐debenzylation mechanism, which helped to elucidate the origin of C4‐regioselectivity in this metal‐free Chichibabin‐type phosphonylation.

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Metal-free site selective cross-coupling of pyridines with secondary phosphine chalcogenides using acylacetylenes as oxidants

Cited by 29 publications

References 24 publications

Recent Advances in the Construction of Phosphorus‐Substituted Heterocycles, 2009–2019

Recent Advances in the Construction of Phosphorus‐Substituted Heterocycles, 2009–2019

Electron-Deficient Acetylenes as Three-Modal Adjuvants in SNH Reaction of Pyridinoids with Phosphorus Nucleophiles

Chichibabin‐Type Phosphonylation of 2‐(Hetero)aryl Pyridines: Selective Synthesis of 4‐Phosphinoyl Pyridines via an Activated N‐Benzylpyridinium Salt

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