Palladium-catalyzed aminocarbonylation of halo-substituted 7-azaindoles and other heteroarenes using chloroform as a carbon monoxide source

Kannaboina, Prakash; Raina, Gaurav; Kumar, K. Raghavendra; Das, Parthasarathi

doi:10.1039/c7cc04339b

Cited by 55 publications

(16 citation statements)

References 64 publications

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“…[6] Since then, many excellent works have been achieved by the groups of Beller, [7] Buchwald, [8] Jiao, [9] Li, [10] and others. [11] This strategy has become ap owerful tool to synthesize amides,o wing to the unique ability of CO serving as an excellent carbonyl source.B ut the current methods are reaching their inherent limits,a nd it is necessary to develop new methods for amide synthesis.…”

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confidence: 99%

Intermolecular C−H Amidation of (Hetero)arenes to Produce Amides through Rhodium‐Catalyzed Carbonylation of Nitrene Intermediates

et al. 2019

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Amide bond formation is one of the most important reactions in organic chemistry because of the widespread presence of amides in pharmaceuticals and biologically active compounds.E xisting methods for amides synthesis are reaching their inherent limits.Described herein is anovel rhodiumcatalyzedthree-component reaction to synthesizeamides from organic azides,c arbon monoxide,a nd (hetero)arenes via nitrene-intermediates and direct CÀHfunctionalization. Notably,the reaction proceeds in an intermolecular fashion with N 2 as the only by-product, and either directing groups nor additives are required. The computational and mechanistic studies showt hat the amides are formed via ak ey Rh-nitrene intermediate.

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confidence: 99%

Intermolecular C−H Amidation of (Hetero)arenes to Produce Amides through Rhodium‐Catalyzed Carbonylation of Nitrene Intermediates

et al. 2019

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“…Similar type of reaction mechanism was mentioned in various transformations for the insertion of carbon monoxide. Palladium catalysed aroylation of NH‐sulfoximines (Scheme 57<xschr57), aminocarbonylation of amines (Scheme ), aminocarbonylation of tetrazoles (Scheme ), aminocarbonylation of indoles (Scheme ) and aminocarbonylation of imidazopyridines (Scheme ) has been established using CHCl 3 as carbonyl source.…”

Section: Reaction Solvents As Precursors For the Installation Of Key mentioning

confidence: 99%

Reaction Medium as the Installing Reservoir for Key Functionalities in the Molecules

2019

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The solvent is an important entity in a chemical reaction, generally, required for the effective collision of the reactant molecules. By looking at the chemical nature, physic-chemical properties, and more importantly, smart selection, reaction solvents attract synthetic chemists for their effective use as reagents in a chemical reaction. For the installation of small key functionalities in the molecules, reaction solvents provide attractive, atom-economical, greener, and also less costly alternatives to other reagent-based strategies. For instance, particular reaction solvents can serve as a multipurpose building block for various units, such as O,

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“…The in situ ‐generated CO from CHCl 3 and a base has been used in various organic reactions such as carboxylation, carbonylative coupling, aminocarbonylations, Heck‐type domino cyclization, and carbonylative Sonogashira coupling . Recently, one of us has elegantly demonstrated the application of this methodology (chloroform as CO surrogates) in aminocarbonylation of 7‐azaindole and imidazopyridines, leading to the synthesis of biologically important aminocarbonyl‐functionalized 7‐azaindole and 2‐amidoimidazo[1,2‐ a ]pyridines . However, all catalysts were generated in situ and high loading of the catalyst was required.…”

Section: Introductionmentioning

confidence: 99%

“…[35] Recently, one of us has elegantly demonstrated the application of this methodology (chloroform as CO surrogates) in aminocarbonylation of 7-azaindole and imidazopyridines, leading to the synthesis of biologically important aminocarbonyl-functionalized 7-azaindole and 2-amidoimidazo [1,2-a]pyridines. [36,37] However, all catalysts were generated in situ and high loading of the catalyst was required.…”

Section: Introductionmentioning

confidence: 99%

Carbonylative Suzuki coupling reactions catalyzed by ONO pincer–type Pd(II) complexes using chloroform as a carbon monoxide surrogate

Layek

Agrahari

Ganguly

et al. 2020

Applied Organom Chemis

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Benzoylhydrazone Schiff base–ligated three new ONO pincer–type palladium(II) complexes, [(PdL1(PPh3)] (1), [(PdL2(PPh3)] (2), and [(PdL3(PPh3)] (3), were synthesized by the reaction of the respective ligand, N‐(2‐hydroxybenzylidene)benzohydrazide (HL1), N‐(2‐hydroxy‐3‐methoxybenzylidene)benzohydrazide (HL2), or N‐(5‐bromo‐2‐hydroxybenzylidene) benzohydrazide (HL3), with Pd(OAc)2 and PPh3 in methanol and isolated as air‐stable reddish‐orange crystalline solids in high yields (78%–83%). All three complexes were fully characterized by elemental analysis, Fourier‐transform infrared spectroscopy, UV–Visible, 1H nuclear magnetic resonance (NMR), 13C{1H} NMR, and 31P{1H} NMR spectroscopic studies. The molecular structure of all three complexes was established unambiguously by single‐crystal X‐ray diffraction studies which revealed a distorted square planar geometry of all three complexes. The ONO pincer–type ligands occupied three coordination sites at the palladium, while the fourth site is occupied by the monodentate triphenylphosphine ligand. The catalytic potential of all three complexes was explored in the carbonylative Suzuki coupling of aryl bromides and iodides with arylboronic acids to yield biaryl ketones, using CHCl3 as the source of carbonyl. The reported protocol is convenient and safe as it obviates the use of carbon monoxide (CO) balloons or pressured CO reactors which are otherwise needed for the carbonylation reactions. The methodology has been successfully applied to the synthesis of two antineoplastic drugs, namely, phenstatin and naphthylphenstatin, in good yields (81% and 85%, respectively). Under the optimized reaction conditions, complex 2 exhibited the best catalytic activity in the carbonylative Suzuki couplings. The reported catalysts have wide reaction scope with good functional group tolerance. All catalysts could be retrieved from the reaction after completion and recycled up to three times with insignificant loss in the catalytic activity.

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Palladium-catalyzed aminocarbonylation of halo-substituted 7-azaindoles and other heteroarenes using chloroform as a carbon monoxide source

Cited by 55 publications

References 64 publications

Intermolecular C−H Amidation of (Hetero)arenes to Produce Amides through Rhodium‐Catalyzed Carbonylation of Nitrene Intermediates

Intermolecular C−H Amidation of (Hetero)arenes to Produce Amides through Rhodium‐Catalyzed Carbonylation of Nitrene Intermediates

Reaction Medium as the Installing Reservoir for Key Functionalities in the Molecules

Carbonylative Suzuki coupling reactions catalyzed by ONO pincer–type Pd(II) complexes using chloroform as a carbon monoxide surrogate

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