BF3-Mediated Oxidative Cross-Coupling of Pyridines with Alkynyllithium Reagents and Further Reductive Functionalizations of the Pyridine Scaffold

León, Thierry; Quinio, Pauline; Chen, Quan; Knöchel, Paul

doi:10.1055/s-0033-1341235

Cited by 10 publications

(3 citation statements)

References 4 publications

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“…Excellent regioselectivity and broad range of functional group tolerance make these procedures very versatile for the synthesis of polyfunctional pyridine scaffolds. Interestingly, this approach does not require transition metal catalysts for these types of C−C coupling reactions, the obtained results are shown in Scheme 22 [88–89] …”

Section: Functionalization Of Pyridine and Quinoline Scaffolds Used B...mentioning

confidence: 88%

“…Interestingly, this approach does not require transition metal catalysts for these types of CÀ C coupling reactions, the obtained results are shown in Scheme 22. [88][89] Using n-BuLi-LiPM chiral complex with 2-chloropyridine 95 substates at À 78 °C in dry hexane, the Ruiz-López group demonstrated regio-and enantioselective control experiments that allowed the formation of pyridyl methyl alcohol 97 with a moderate yield and enantioselectivity. Trapping with TMSCl under the previously discussed similar reaction conditions produced silylated pyridine in a superb yield (Scheme 23).…”

Section: Functionalization Of Pyridine and Quinoline Scaffolds Used B...mentioning

confidence: 99%

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Functionalization of Pyridine and Quinoline Scaffolds by Using Organometallic Li‐, Mg‐ and Zn‐Reagents

Dhayalan¹,

Sharma

Chatterjee

et al. 2023

Eur J Org Chem

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This Review discusses the various methods for functionalizing pyridine and quinoline scaffolds, including direct selective metalation (DoM), halogen/metal exchange reactions, Li, Mg, and Zn insertion, and trans‐metalation approaches, which are then followed by cross‐coupling reactions of the Kumada or Negishi types. Selective deprotonation of aryl or pyridyl/quinolinyl derivatives can be performed using n‐BuLi, LDA, and TMP‐based different organolithium, ‐magnesium, and ‐zinc reagents. The functionalized pyridine and quinoline‐based heterocyclic compounds were prepared by selectively deprotonating with presenting a directing functional group substituted pyridine/quinoline analogues in the presence of TMP‐bases (TMP−Li, Mg, Zn reagents). Different aryl or alkyl Li, Mg, and Zn reagents with electron‐donating and electron‐withdrawing substituents undergo transition metal‐catalyzed C(sp2)−C(sp2) and C(sp2)−C(sp3) types of cross‐coupling reactions with pyridine/quinoline halides under mild conditions with the sustainable process producing complex N‐heterocycles. Using moderate and sustainable reaction conditions, sensitive functional group tolerance, and inexpensive and low toxic chemicals, highly functionalization of pyridine and quinoline‐based bioactive therapeutic scaffolds and natural products was accomplished. Therefore, in this article, we provide a succinct overview of the numerous synthetic strategies and practical methods used by various authors between 2010 and 2023 to functionalize pyridine and quinoline analogues using diverse Li, Mg, and Zn organometallic reagents.

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Section: Functionalization Of Pyridine and Quinoline Scaffolds Used B...mentioning

confidence: 88%

Section: Functionalization Of Pyridine and Quinoline Scaffolds Used B...mentioning

confidence: 99%

Functionalization of Pyridine and Quinoline Scaffolds by Using Organometallic Li‐, Mg‐ and Zn‐Reagents

Dhayalan¹,

Sharma

Chatterjee

et al. 2023

Eur J Org Chem

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“…2-Phenylpyridines and 2,2′-bipyridines are widely used ligands for photocatalysts of Ir(III) and Ru(II) . To obtain alkyl- and arylpyridines, Minisci reactions of pyridines; transition metal-catalyzed couplings of halopyridines (Suzuki–Miyaura, Negishi, Kumada–Tamao–Corriu, Kochi–Fürstner reactions, and Ni-catalyzed reductive coupling reactions developed by Weix et al) or 2-pyridyl ammonium salts; C–H arylations, alkylations, and alkenylations of pyridines; BF 3 -promoted additions of Grignard or alkynyllithium reagents to pyridines followed by rearomatizations; and S N Ar reactions of Grignard reagents toward 4-cyanopyridines (assisted by BF 3 ), halopyridines (assisted by triphosgene), or pyridine-2-sulfinate were developed. 2,2′-Bipyridines were prepared by reductive coupling of chloropyridines , and phosphorus ligand coupling .…”

Section: Introductionmentioning

confidence: 99%

Purple Light-Promoted Coupling of Bromopyridines with Grignard Reagents via SET

Lei,

Wang,

et al. 2024

J. Org. Chem.

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Alkyl- and arylpyridines and 2,2′-bipyridines are conventionally prepared by Minisci reactions of pyridines and transition metal-catalyzed coupling reactions of halopyridines. Herein, purple light-promoted radical coupling reactions of 2- or 4-bromopyridines with Grignard reagents in Et2O or a mixture of Et2O and tetrahydrofuran in regular glassware without the need for a transition metal catalyst were disclosed for the first time. Methyl, primary and secondary alkyl, cycloalkyl, aryl, heteroaryl, pyridyl, and alkynyl Grignard reagents were compatible with the protocol. As a result, alkyl- and arylpyridines and 2,2′-bipyridines were easily prepared. Single electron transfer from the Grignard reagent to bromopyridine was stimulated by purple light. An electron extruded from the dimerization of the Grignard reagent worked as the catalyst. Light on/off experiments indicated that constant irradiation was required for product formation. Studies of radical clock substrates verified the involvement of a pyridyl radical from bromopyridine and the noninvolvement of an alkyl or aryl radical from the Grignard reagent. The available proof supports a photoinduced SRN mechanism for the new coupling reactions.

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Additive‐Controlled Switchable Selectivity from Cyanobenzenes to 2‐Alkynylpyridines: Ruthenium(II)‐Catalyzed [2+2+2] Cycloadditions of Diynes and Alkynylnitriles

et al. 2018

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A highly efficient additive‐dependent chemoselective protocol for the synthesis of fused cyanoarenes and 2‐alkynylpyridines has been developed by the reaction of 1,6‐diynes with alkynylnitriles using chloro(pentamethylcyclopentadienyl) (cyclooctadiyne)ruthenium(II) as catalyst in dimethoxyethane (DME). The course of the reaction can be drastically altered simply by adding a catalytic amount of AgOTf as an additive resulting in a comprehensive shift in product formation from cyanoarenes to 2‐alkynylpyridines. Theoretical studies clearly indicate that the neutral Ru‐complex is responsible for the formation of cyanobenzenes, whereas the in situ generated cationic Ru‐complex plays a crucial role in the 2‐alkynylpyridines formation.magnified image

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BF3-Mediated Oxidative Cross-Coupling of Pyridines with Alkynyllithium Reagents and Further Reductive Functionalizations of the Pyridine Scaffold

Cited by 10 publications

References 4 publications

Functionalization of Pyridine and Quinoline Scaffolds by Using Organometallic Li‐, Mg‐ and Zn‐Reagents

Functionalization of Pyridine and Quinoline Scaffolds by Using Organometallic Li‐, Mg‐ and Zn‐Reagents

Purple Light-Promoted Coupling of Bromopyridines with Grignard Reagents via SET

Additive‐Controlled Switchable Selectivity from Cyanobenzenes to 2‐Alkynylpyridines: Ruthenium(II)‐Catalyzed [2+2+2] Cycloadditions of Diynes and Alkynylnitriles

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