2-Halopyridines in the triple reaction in the P /KOH/DMSO system to form tri(2-pyridyl)phosphine: Experimental and quantum-chemical dissimilarities

Малышева, С. Ф.; Kuimov, Vladimir A.; Trofimov, A. B.; Белогорлова, Н. А.; Litvintsev, Yurii I.; Belogolova, Alexandra M.; Гусарова, Н. К.; Трофимов, Б. А.

doi:10.1016/j.mencom.2018.09.006

Cited by 14 publications

(5 citation statements)

References 37 publications

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“…Therefore in the laboratories of Trofimov a protocol for the synthesis of phosphines was developed starting directly from red or white phosphorus. [152][153][154] This method based on the Trofimov-Gusarova reaction conditions is assumed to proceed via PꟷP bond cleavage by the superbasic media (KOH/DMSO). Nucleophilic attack of in situ generated polyphosphide 226 and polyphosphinite 227 particles towards 2-bromopyridine 229 can then lead to e.g.…”

Section: Synthesis Of Encapsulating Preligandsmentioning

confidence: 99%

“…tri(2-pyridyl)phosphine 232 or its phosphine oxide 233 (Scheme 71). [154] Using red phosphorus and the right electrophile can suppress the formation of phosphine oxides.…”

Section: Synthesis Of Encapsulating Preligandsmentioning

confidence: 99%

“…Scheme 71: Mechanism of Trofimov-Gusarova reaction using tri(2-pyridyl)phosphine as an example [154] A similar approach was now developed and optimized for 6-bromo-2,2'-bipyridine. The preligand 212 could be isolated in 46% yield (Scheme 72).…”

Section: Synthesis Of Encapsulating Preligandsmentioning

confidence: 99%

“…It has been shown that using chlorides instead of bromides suppresses the formation of phosphine oxides during Trofimov-Gusarova reaction. [154] Furthermore, 6-chloro-4,4'-dimethyl-2,2'bipyridine is easy to synthesize via a two-step procedure of oxidation (77% [157] ) and chlorination (80% [157] ) without the need of palladium catalysis nor toxic stannanes (Scheme 75).…”

Section: Synthesis Of Encapsulating Preligandsmentioning

confidence: 99%

“…The syntheses were carried out using a modified literature procedure. [152][153][154] An oven-dried 100mL three-necked round-bottom flask was equipped with a stirring bar, reflux condenser (+Tee connector with bubbler and nitrogen-inlet) and an adapter with stopcock and connector (nitrogen-side-inlet). The bubbler was connected with an absorbent bottle containing saturated aqueous CuSO4*5H2O solution via tubing.…”

Section: Compound 212mentioning

confidence: 99%

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Tuning the donor properties of bipyridyl-substituted phosphines by metal ion encapsulation & Photocatalytic synthesis of 6H-benzo[c]chromenes from S-aryl sulfonium salts

Karreman¹

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Lewis acid catalysis vs. Brønsted acid catalysisWith the corresponding costs for ligands and noble metals, the question arises why one cannot simply use proton catalysis instead (Brønsted acid catalysis). A proton is after all isolobal to the LAu + and Hg 2+ fragments. An evident difference is the contrasting hardness according to the Pearson concept. [6] Protons are hard Lewis acids, while mentioned metal fragments are soft Lewis acids. This difference leads to the fact that protons often need harsh reaction conditions and are less selective. The softer metal fragments, however, have higher affinity to soft substrates and therefore require less harsh conditions and react in higher selectivity. Besides this evident difference, the use of metal fragments also allows the possibility of stabilizing carbene-like intermediates and to unlock their reactivity. In the case of gold(I), this topic is highly controversial, and resonances of gold carbenes or gold-stabilized carbocations are discussed (→"carbenoid" [6] or "carbene" [11] , Scheme 2). [11,12] Scheme 2: Gold carbene [11] Scheme 14:Chalk-Harrod mechanism [36] The latter mechanism is composed of oxidative addition (I) followed by ligand association (II), insertion (III) and reductive elimination (IV). As a side reaction, mainly β-hydride elimination is present. Because of its ability to activate inert bonds, platinum(II) is also used in the activation of methane, which represents a classic example of CꟷH activation (Shilov system). [37] Methanol and chloromethane can Scheme 20: Oxidation of phosphines to phosphine selenides [55] Since the J-coupling constant contains information about the electronic environment, bonding situation and hybridization of 31 P (I = ½) and 77 Se (I = ½) via the Fermi contact interaction, it is also strongly influenced by the polarization of the PꟷSe bond. If electron pushing substituents are chosen on the phosphorus, the coupling constant 1 JPSe decreases, while electron withdrawing substituents result in high coupling constants. In other words, the coupling constant decreases as the basicity of the corresponding unoxidized phosphine increases (Scheme 21).

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Section: Synthesis Of Encapsulating Preligandsmentioning

confidence: 99%

“…tri(2-pyridyl)phosphine 232 or its phosphine oxide 233 (Scheme 71). [154] Using red phosphorus and the right electrophile can suppress the formation of phosphine oxides.…”

Section: Synthesis Of Encapsulating Preligandsmentioning

confidence: 99%

Section: Synthesis Of Encapsulating Preligandsmentioning

confidence: 99%

Section: Synthesis Of Encapsulating Preligandsmentioning

confidence: 99%

Section: Compound 212mentioning

confidence: 99%

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Tuning the donor properties of bipyridyl-substituted phosphines by metal ion encapsulation & Photocatalytic synthesis of 6H-benzo[c]chromenes from S-aryl sulfonium salts

Karreman¹

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Superbase‐Assisted Selective Synthesis of Triarylphosphines from Aryl Halides and Red Phosphorus: Three Consecutive Different S_NAr Reactions in One Pot

et al. 2019

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Aryl halides, ArX (Ar = Ph, 2‐, 3‐ and 4‐Tol, 1‐ and 2‐Np, 4‐C6H4CONH2; X = F, Cl, Br), rapidly and exothermically (100–180 °C, 0.5–2 h) react with red phosphorus in superbase systems KOH/L, where L is a polar nonhydroxylic complexing solvent (ligand), such as NMP, DMSO, HMPA, to afford the corresponding triarylphosphines (Ar3P) in up to 74 % yield (for X = F). Thus, three consecutive reactions of SNAr (aromatic nucleophilic substitution) to form the three C(sp2)–P bonds are realized in one pot. The synthesis is mostly chemoselective (with rare exception): neither mono‐ nor diphosphines have been isolated. The best results were attained when aryl fluorides were treated with red phosphorus (Pn) in the KOH/NMP superbase system. This environmentally friendly, PCl3‐free synthesis of Ar3P from available starting materials opens an easy and straightforward access to triarylphosphines, which are important ligands, synthetic auxiliaries, and components of high‐tech‐ and medicinally oriented complexes.

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Synthesis of nitrogen, phosphorus, selenium and sulfur-containing heterocyclic compounds – Determination of their carbonic anhydrase, acetylcholinesterase, butyrylcholinesterase and α-glycosidase inhibition properties

Gülçın

Трофимов

Kaya

et al. 2020

Bioorganic Chemistry

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2-Halopyridines in the triple reaction in the P /KOH/DMSO system to form tri(2-pyridyl)phosphine: Experimental and quantum-chemical dissimilarities

Cited by 14 publications

References 37 publications

Tuning the donor properties of bipyridyl-substituted phosphines by metal ion encapsulation & Photocatalytic synthesis of 6H-benzo[c]chromenes from S-aryl sulfonium salts

Tuning the donor properties of bipyridyl-substituted phosphines by metal ion encapsulation & Photocatalytic synthesis of 6H-benzo[c]chromenes from S-aryl sulfonium salts

Superbase‐Assisted Selective Synthesis of Triarylphosphines from Aryl Halides and Red Phosphorus: Three Consecutive Different S_NAr Reactions in One Pot

Synthesis of nitrogen, phosphorus, selenium and sulfur-containing heterocyclic compounds – Determination of their carbonic anhydrase, acetylcholinesterase, butyrylcholinesterase and α-glycosidase inhibition properties

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2-Halopyridines in the triple reaction in the P /KOH/DMSO system to form tri(2-pyridyl)phosphine: Experimental and quantum-chemical dissimilarities

Cited by 14 publications

References 37 publications

Tuning the donor properties of bipyridyl-substituted phosphines by metal ion encapsulation & Photocatalytic synthesis of 6H-benzo[c]chromenes from S-aryl sulfonium salts

Tuning the donor properties of bipyridyl-substituted phosphines by metal ion encapsulation & Photocatalytic synthesis of 6H-benzo[c]chromenes from S-aryl sulfonium salts

Superbase‐Assisted Selective Synthesis of Triarylphosphines from Aryl Halides and Red Phosphorus: Three Consecutive Different SNAr Reactions in One Pot

Synthesis of nitrogen, phosphorus, selenium and sulfur-containing heterocyclic compounds – Determination of their carbonic anhydrase, acetylcholinesterase, butyrylcholinesterase and α-glycosidase inhibition properties

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Superbase‐Assisted Selective Synthesis of Triarylphosphines from Aryl Halides and Red Phosphorus: Three Consecutive Different S_NAr Reactions in One Pot