Copper‐Catalyzed Reaction of Secondary Propargylamines with Ethyl Buta‐2,3‐dienoate for the Synthesis of 1,6‐Dihydropyridines

Liu, Chao; Wang, Gaigai; Wang, Yuqing; Pereshivko, Olga P.; Peshkov, Vsevolod A.

doi:10.1002/ejoc.201801227

Cited by 10 publications

(7 citation statements)

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“…Propargylamines , are essential precursors in the synthesis of high value products, including isoindolines, oxazolidines, pyridones, , and alkaloids. − Following our work on Cu(II) protocols in A 3 couplings, , we selected cyclohexanecarboxaldehyde, pyrrolidine, and phenylacetylene as model substrates. Each catalytic reaction was performed in duplicate, and reproducibility and yields are given as an average with deviations of <10%.…”

Section: Resultsmentioning

confidence: 99%

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Room-Temperature Cu(II) Radical-Triggered Alkyne C–H Activation

Devonport

Sully

Boudalis

et al. 2021

JACS Au

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A dimeric Cu(II) complex [Cu(II) 2 L 2 (μ 2 -Cl)Cl] (1) built from an asymmetric tridentate ligand (2-(((2aminocyclohexyl)imino)methyl)-4,6-di-tert-butylphenol) and weakly coordinating anions has been synthesized and structurally characterized. In dichloromethane solution, 1 exists in a monomeric [Cu(II)LCl] (1′) (85%)−dimeric (1) (15%) equilibrium, and cyclic voltammetry (CV) and electron paramagnetic resonance (EPR) studies indicate structural stability and redox retention. Addition of phenylacetylene to the CH 2 Cl 2 solution populates 1′ and leads to the formation of a transient radical species. Theoretical studies support this notion and show that the radical initiates an alkyne C−H bond activation process via a fourmembered ring (Cu(II)−O•••H−C alkyne ) intermediate. This unusual C−H activation method is applicable for the efficient synthesis of propargylamines, without additives, within 16 h, at low loadings and in noncoordinating solvents including late-stage functionalization of important bioactive molecules. Single-crystal X-ray diffraction studies, postcatalysis, confirmed the framework's stability and showed that the metal center preserves its oxidation state. The scope and limitations of this unconventional protocol are discussed.

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Section: Resultsmentioning

confidence: 99%

“…Propargylamines 59,60 are essential precursors in the synthesis of high value products, including isoindolines, 61 oxazolidines, 62 pyridones, 63,64 and alkaloids. 65−67 Following our work on Cu(II) protocols in A 3 couplings, 23,24 we selected cyclohexanecarboxaldehyde, pyrrolidine, and phenylacetylene as model substrates.…”

Section: ■ Introductionmentioning

confidence: 99%

Room-Temperature Cu(II) Radical-Triggered Alkyne C–H Activation

Devonport

Sully

Boudalis

et al. 2021

JACS Au

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“…1,6‐Dihydropyridine derivatives 153 were synthesized by the copper(I) bromide‐catalyzed one‐pot two‐step reaction of propargylamines, which are generated via A 3 coupling, with ethyl buta‐2,3‐dienoate ( 152 ) (Scheme 46). [98] A variety of electron‐withdrawing and electron‐donating aryl‐substituted alkynes successfully participated in the reaction. A plausible mechanism for this transformation begins with the formation of the propargylamines 4 followed by nucleophilic addition of the allene 152 to yield enyne intermediates 154 .…”

Section: Synthesis Of Six‐membered N‐heterocyclesmentioning

confidence: 99%

A³ Coupling Reaction in the Synthesis of Heterocyclic Compounds

2020

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In recent years, the transition‐metal catalyzed three‐component coupling of an aldehyde, an alkyne and an amine, commonly called A3 coupling has become a powerful tool in organic synthesis. The aim of this review is to give a general overview of A3 coupling utility in the synthesis of heterocycles, highlighting the variety of compounds that can be directly accessed from single reactions. The diverse A3 coupling based methodologies that have been developed for the synthesis of N,O,S‐heterocycles are presented, emphasizing the influence of the reaction conditions and the use of additional reagents in the outcome of the transformations.

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“…15,16 Interestingly, Peshkov, Pereshivko, and co-workers studied a copper-catalyzed protocol for the synthesis of 1,6-dihydropyridines from propargylic amines and ethyl buta-2,3-dienoate. 17 In their study, 6-endo-dig cyclization of N-propargylated enamino esters generated in situ delivered dihydropyridines. As part of our continuing efforts to develop efficient methods for constructing highly functionalized privileged heterocycles, 18,19 we aimed to develop an allenoate-based method for the ready assembly of polysubstituted pyrroles.…”

Section: Letter Syn Lettmentioning

confidence: 99%