Metal-free SHN cross-coupling of pyridines with phosphine chalcogenides: polarization/deprotonation/oxidation effects of electron-deficient acetylenes

2021 ◽  
Vol 45 (14) ◽  
pp. 6206-6219
Author(s):  
Pavel A. Volkov ◽  
Anton A. Telezhkin ◽  
Kseniya O. Khrapova ◽  
Nina I. Ivanova ◽  
Alexander I. Albanov ◽  
...  
Keyword(s):  
Cross Coupling ◽  
Metal Free ◽  
Reaction Proceeds ◽  
Phosphine Chalcogenides

Terminal acylacetylenes act as trimodal auxiliaries in SHN cross-coupling of pyridines with phosphine chalcogenides. The reaction proceeds via phosphorylation of the pyridine 2 position followed by 2 → 4-migration of phosphoryl moieties.

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

Molecules ◽  
2021 ◽  
Vol 26 (22) ◽  
pp. 6824
Author(s):  
Boris A. Trofimov ◽  
Pavel A. Volkov ◽  
Anton A. Telezhkin
Keyword(s):  
Nucleophilic Addition ◽  
Pyridine Ring ◽  
Cross Coupling ◽  
Secondary Phosphine ◽  
Metal Free ◽  
Secondary Phosphine Chalcogenides ◽  
Heterocyclic Moiety ◽  
Acid Esters ◽  
Phosphine Chalcogenides

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).

Oxidative metal-free cross-coupling of secondary phosphine chalcogenides and benzenediols: Synthesis of phosphinochalcogenoic O-diesters

2012 ◽  
Vol 23 (4) ◽  
pp. 322-328 ◽  
Author(s):  
Nina K. Gusarova ◽  
Pavel A. Volkov ◽  
Nina I. Ivanova ◽  
Ludmila I. Larina ◽  
Boris A. Trofimov
Keyword(s):  
Cross Coupling ◽  
Secondary Phosphine ◽  
Metal Free ◽  
Secondary Phosphine Chalcogenides ◽  
Phosphine Chalcogenides

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

2018 ◽  
Vol 54 (27) ◽  
pp. 3371-3374 ◽  
Author(s):  
Boris A. Trofimov ◽  
Pavel A. Volkov ◽  
Kseniya O. Khrapova ◽  
Anton A. Telezhkin ◽  
Nina I. Ivanova ◽  
...  
Keyword(s):  
Cross Coupling ◽  
Secondary Phosphine ◽  
Metal Free ◽  
Mild Conditions ◽  
Secondary Phosphine Chalcogenides ◽  
Site Selective ◽  
Phosphine Chalcogenides

Pyridines are easily cross-coupled with secondary phosphine chalcogenides in the presence of acylphenylacetylenes under mild conditions to afford 4-chalcogenophosphorylpyridines.

ChemInform Abstract: Oxidative Metal-Free Cross-Coupling of Secondary Phosphine Chalcogenides and Benzenediols: Synthesis of Phosphinochalcogenoic O-Diesters.

ChemInform ◽  
2012 ◽  
Vol 43 (46) ◽  
pp. no-no
Author(s):  
Nina K. Gusarova ◽  
Pavel A. Volkov ◽  
Nina I. Ivanova ◽  
Ludmila I. Larina ◽  
Boris A. Trofimov
Keyword(s):  
Cross Coupling ◽  
Secondary Phosphine ◽  
Metal Free ◽  
Secondary Phosphine Chalcogenides ◽  
Phosphine Chalcogenides

Metal-Free Photoredox-Catalyzed C–H/C–H Coupling of Arenes Enabled by Interrupted Pummerer Activation

2019 ◽  
Author(s):  
Miles Aukland ◽  
Mindaugas Šiaučiulis ◽  
Adam West ◽  
Gregory Perry ◽  
David Procter
Keyword(s):  
Natural Product ◽  
Selective Reduction ◽  
Cross Coupling ◽  
One Pot ◽  
Complex Molecules ◽  
Pummerer Reaction ◽  
Metal Free ◽  
Bond Forming ◽  
Coupling Partner ◽  
Bioactive Natural Product

<p>Aryl–aryl cross-coupling constitutes one of the most widely used procedures for the synthesis of high-value materials, ranging from pharmaceuticals to organic electronics and conducting polymers. The assembly of (hetero)biaryl scaffolds generally requires multiple steps; coupling partners must be functionalized before the key bond-forming event is considered. Thus, the development of selective C–H arylation processes in arenes, that side-step the need for prefunctionalized partners, is crucial for streamlining the construction of these key architectures. Here we report an expedient, one-pot assembly of (hetero)biaryl motifs using photocatalysis and two non-prefunctionalized arene partners. The approach is underpinned by the activation of a C–H bond in an arene coupling partner using the interrupted Pummerer reaction. A unique pairing of the organic photoredox catalyst and the intermediate dibenzothiophenium salts enables highly selective reduction in the presence of sensitive functionalities. The utility of the metal-free, one-pot strategy is exemplified by the synthesis of a bioactive natural product and the modification of complex molecules of societal importance.</p>

scholarly journals Transition-Metal-Free Cross-Coupling of Aryl Halides with Arylstannanes

2021 ◽  
Author(s):  
Qing He ◽  
Wenli Wang ◽  
Yong Liang ◽  
Zunting Zhang ◽  
Stanislaw F. Wnuk
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Aryl Halides ◽  
Metal Free

scholarly journals Nickel-Catalyzed Asymmetric Reductive Cross-Coupling of α-Chloroesters with (Hetero)Aryl Iodides

2021 ◽  
Author(s):  
Travis DeLano ◽  
Sara Dibrell ◽  
Caitlin R. Lacker ◽  
Adam Pancoast ◽  
Kelsey Poremba ◽  
...  
Keyword(s):  
Cross Coupling ◽  
Mild Conditions ◽  
Aryl Iodides ◽  
Reaction Proceeds

An asymmetric reductive cross-coupling of α-chloroesters and (hetero)aryl iodides is reported. This nickel-catalyzed reaction proceeds with a chiral BiOX ligand under mild conditions, affording α-arylesters in good yields and enantioselectivities....

scholarly journals Metal-free oxidative cross-coupling enabled practical synthesis of atropisomeric QUINOL and its derivatives

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Peng-Ying Jiang ◽  
Kai-Fang Fan ◽  
Shaoyu Li ◽  
Shao-Hua Xiang ◽  
Bin Tan
Keyword(s):  
Asymmetric Catalysis ◽  
Kinetic Resolution ◽  
Academic Research ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Industrial Applications ◽  
Lewis Base ◽  
Production Costs ◽  
Metal Free ◽  
Base Catalysts

AbstractAs an important platform molecule, atropisomeric QUINOL plays a crucial role in the development of chiral ligands and catalysts in asymmetric catalysis. However, efficient approaches towards QUINOL remain scarce, and the resulting high production costs greatly impede the related academic research as well as downstream industrial applications. Here we report a direct oxidative cross-coupling reaction between isoquinolines and 2-naphthols, providing a straightforward and scalable route to acquire the privileged QUINOL scaffolds in a metal-free manner. Moreover, a NHC-catalyzed kinetic resolution of QUINOL N-oxides with high selectivity factor is established to access two types of promising axially chiral Lewis base catalysts in optically pure forms. The utility of this methodology is further illustrated by facile transformations of the products into QUINAP, an iconic ligand in asymmetric catalysis.

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