One-Step Synthesis of 3,5-Disubstituted-2-pyridylpyrroles from the Condensation of 1,3-Diones and 2-(Aminomethyl)pyridine

Klappa, Jamie J.; Rich, and Autumn E.; McNeill, Kristopher

doi:10.1021/ol017147v

Cited by 77 publications

(71 citation statements)

References 17 publications

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“…There are just a few examples of the synthesis of pyridylpyrroles, including the photolysis of pyridylchlorodiazirines in the presence of 1-azabuta-1,3-dienes, [14] heterocyclization of acetylene with oximes of acetylpyridines [15][16][17][18] and dimethyl glyoxime [19] (the Trofimov reaction) [20] and the Paal-Knorr high-temperature condensation (170-190°C) of 1,3-diketones with 2-(aminomethyl)pyridine. [21] Of these methods, none is an obvious candidate to be simply modified for the synthesis of dipyrrolylpyridines. Although the ketoxime-acetylene route may look most appropriate for that, the specificity of oximes of diacetylpyridines, including their enhanced chelating power and that of the intermediates, [22] could seriously interfere with the synthesis.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Spectral Properties of Bis(pyrrol‐2‐yl)pyridines

et al. 2005

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Keywords: Acetylene / Heterocycles / X-ray absorption spectroscopy / UV/Vis spectroscopy / Fluorescence spectroscopy (10), and 2,6-dimethyl-3-(pyrrol-2-yl)-5-[2-(1-vinylpyrrol-2-yl)]pyridine (11) have been synthesized from the oximes of the corresponding diacetylpyridines in a one-pot procedure by treatment with acetylene in MOH/DMSO systems (M = Li, K) at 80-140°C under pressures of 25-30 atm, thus illustrating the applicability and general character of the reaction for synthesis of diverse dipyrrole-pyridine assemblies and their N-vinyl and acetyl derivatives. A stable 4·DMSO

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Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Spectral Properties of Bis(pyrrol‐2‐yl)pyridines

et al. 2005

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“…13,14 Although there are only a few metal complexes of pyridylpyrrolide in literature, it has been shown that this ligand can stabilize high-valent, polyhydride iridium complexes. [15][16][17][18][19][20][21][22][23] The pyridylpyrrolide derivative that will be implemented in this work is the ligand 3,5-bis(trifluoromethyl)-2-(2′-pyridyl)pyrrole [(X)(L)] (X = H + or K + ).…”

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confidence: 99%

An iridium–pyridylpyrrolide complex exhibiting reversible binding of H2

et al. 2012

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“…In addition, selectivity for anti-Markovnikov over Markovnikov products (ca. Deprotonation of dmpp-H (3) [10] with KH in THF yielded green dmpp-K (4). However, significantly higher selectivities and turnover numbers (TONs) are needed to make these processes economical, so a broadly tunable system that can be modified both sterically and electronically is likely needed.…”

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confidence: 99%

Intermolecular Hydroarylation of Unactivated Olefins Catalyzed by Homogeneous Platinum Complexes

Luedtke

Goldberg

2008

Angew Chem Int Ed

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The hydroarylation of olefins is a valuable C À C bond forming reaction used to produce alkyl arenes.[1] Olefin hydroarylation can be catalyzed by Lewis acids, but such reactions proceed through a Friedel-Crafts type mechanism involving an intermediary carbocation. Thus, these reactions give predominantly Markovnikov products, and ortho, meta, and para selectivity is determined by the substituents on the aromatic ring. In contrast, the use of transition-metal catalysts can afford different regioselectivities acting via a mechanism of arene CÀH bond activation and olefin insertion.[1] While in the past transition-metal-catalyzed olefin hydroarylation reactions were primarily limited to activated arenes wherein a chelating functionality on the arene was available to assist and direct the C À H bond activation step, [1] recently Ir III and Ru II catalysts have demonstrated hydroarylation with unactivated arenes and olefins. [2,3] Mechanistic and computational studies on these Ir III and Ru II catalysts suggest that the hydroarylation does not proceed through a Friedel-Crafts type activation but through olefin insertion followed by oxidative hydrogen migration. In addition, selectivity for antiMarkovnikov over Markovnikov products (ca. 60:40) was observed. However, significantly higher selectivities and turnover numbers (TONs) are needed to make these processes economical, so a broadly tunable system that can be modified both sterically and electronically is likely needed.One promising metal for olefin hydroarylation is platinum. There is considerable precedent for both arene C À H bond activation and olefin insertion at Pt II ; [4,5] however, attempts at olefin hydroarylation with Pt II have been disappointing.[6] Selectivities consistent with an electrophilic Friedel-Crafts type pathway were observed using a mixed Ag-Pt catalyst system. [7] With a related Pt II catalyst, the hydroarylation of norbornene was reported, but other olefins were found to be unreactive.[8] Finally, tridentate chelation of a tris(pyrazolyl)borate ligand stabilized a potential Pt IV intermediate preventing catalytic turnover.[5] Herein, we describe the rational development of an effective Pt II system for intermolecular hydroarylation with unactivated arenes and olefins and present mechanistic evidence consistent with a pathway involving aryl-olefin insertion and C À H bond oxidative addition at Pt II . While Markovnikov products are favored, anti-Markovnikov products are observed, and the mechanistic insight gained is promising for rational design of more selective and productive Pt II catalysts for these reactions.We recently reported that thermolysis of the five-coordinate Pt IV complexes [(LX)PtMe 3 ] {LX = dtbpp [3,5-di-tertbutyl-2-(2-pyridyl)pyrrolide] (1 a) or dppp [3,5-diphenyl-2-(2-pyridyl)pyrrolide] (1 b)} at 85-100 8C in C 6 D 6 in the presence of C 2 H 4 (9-60 equivalents) led to the release of ethane and methane and formation of Pt II complexes 2 a or 2 b, which contain a cyclometalated substituted pyrrolide group and C 2 H 4 ...

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One-Step Synthesis of 3,5-Disubstituted-2-pyridylpyrroles from the Condensation of 1,3-Diones and 2-(Aminomethyl)pyridine

Cited by 77 publications

References 17 publications

Synthesis, Structure, and Spectral Properties of Bis(pyrrol‐2‐yl)pyridines

Synthesis, Structure, and Spectral Properties of Bis(pyrrol‐2‐yl)pyridines

An iridium–pyridylpyrrolide complex exhibiting reversible binding of H2

Intermolecular Hydroarylation of Unactivated Olefins Catalyzed by Homogeneous Platinum Complexes

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