Palladium‐Catalyzed Aminocarbonylation of Aliphatic Alkenes with <i>N,N</i>‐Dimethylformamide as an In Situ Source of CO

Seidensticker, Thomas; Furst, Marc R. L.; Frauenlob, Robin; Vondran, Johanna; Paetzold, Eckhard; Kragl, Udo; Vorholt, Andreas J.

doi:10.1002/cctc.201500824

Cited by 28 publications

(13 citation statements)

References 61 publications

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“…Replacing methyl formate by dimethylformamide (DMF) was attempted in order to produce amides from alkenes by Vorholt, Seidensticker, Furst, Vondran, and others in 2015 . Acid-catalyzed decomposition of DMF into CO and dimethylamine under acidic conditions is a necessary step but leads to a dead end, the dimethylamine being unable to achieve the nucleophilic attack.…”

Section: Alternative Carbon Monoxide Sources For Carbonylationmentioning

confidence: 99%

Magic of Alpha: The Chemistry of a Remarkable Bidentate Phosphine, 1,2-Bis(di-tert-butylphosphinomethyl)benzene

Vondran

Furst

Eastham³

et al. 2021

Chem. Rev.

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The bidentate phosphine ligand 1,2-bis(di-tert-butylphosphinomethyl)benzene (1,2-DTBPMB) has been reported over the years as being one of, if not the, best ligands for achieving the alkoxycarbonylation of various unsaturated compounds. Bonded to palladium, the ligand provides the basis for the first step in the commercial (Alpha) production of methyl methacrylate as well as very high selectivity to linear esters and acids from terminal or internal double bonds. The present review is an overview covering the literature dealing with the 1,2-DTBPMB ligand: from its first reference, its catalysis, including the alkoxycarbonylation reaction and its mechanism, its isomerization abilities including the highly selective isomerizing methoxycarbonylation, other reactions such as cross-coupling, recycling approaches, and the development of improved, modified ligands, in which some tert-butyl ligands are replaced by 2-pyridyl moieties and which show exceptional rates for carbonylation reactions at low temperatures.

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Section: Alternative Carbon Monoxide Sources For Carbonylationmentioning

confidence: 99%

Magic of Alpha: The Chemistry of a Remarkable Bidentate Phosphine, 1,2-Bis(di-tert-butylphosphinomethyl)benzene

Vondran

Furst

Eastham³

et al. 2021

Chem. Rev.

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“…Construction of amide linkages is one of the most attractive reactions in organic synthesis due to their vast applications in various fields such as peptide synthesis, pharmaceuticals, polymers, agrochemicals and functional materials . Immense importance and demand of amides require developing the environmentally benign approaches for their synthesis . Conventional synthesis of amides relayed on the coupling of activated carboxylic acids with amines .…”

Section: Introductionmentioning

confidence: 99%

Direct Synthesis of Amides from Oxidative Coupling of Benzyl Alcohols or Benzylamines with N‐Substituted Formamides Using a Cu‐Fe‐Based Heterogeneous Catalyst

et al. 2018

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Here we report a highly active and recyclable Cu−Fe based heterogeneous catalytic system for the oxidative coupling of benzyl alcohols as well as benzylamines with N‐substituted formamides. The Cu−Fe Metal Oxide (Cu−Fe MO) catalyst was prepared by a co‐precipitation method and was characterized by X‐ray diffraction ( XRD), X‐ray photoelectron spectroscopy ( XPS), Energy‐dispersive X‐ray spectroscopy (EDS), Field Emission Gun‐Scanning Electron Microscopy (FEG‐SEM) and N2 physical adsorption techniques. The catalytic activity of the as‐prepared Cu−Fe MO catalyst was evaluated towards amidation reactions and a broad spectrum of aromatic amides have been synthesized in good to moderate yields by oxidative coupling of benzyl alcohols or benzylamines bearing various substituents with N‐substituted formamides. The control experiments revealed that the benzyl alcohol or benzylamine gets converted to an acyl radical and on the other side the N‐substituted formamides form an aminyl radical in presence of the catalyst and tert‐Butyl hydroperoxide (TBHP). Successive coupling of the in‐situ generated acyl and aminyl radicals affords the desired product amide. Furthermore, the heterogeneous Cu−Fe MO catalyst recycled for four times towards the amidation of benzyl alcohol and the fidelity of the spent catalyst has been confirmed by XRD analysis.

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“…Transition metal-catalyzed aminocarbonylation of aryl (pseudo)halides or unsaturated compounds (alkenes, alkynes, allenes, dienes, etc.) is a promising alternative for the synthesis of diverse functionalized amides. , Compared with alkoxycarbonylation of alkenes, there are only a few of reports using Pd-catalyzed aminocarbonylation of alkenes and amines which represent an efficient and high atom economical route to produce amides. − Recently, Beller and Cole-Hamilton and co-workers independently reported the Pd-catalyzed aminocarbonylation of alkenes to form linear amides as major products, while Liu and co-workers developed a method to obtain branched amides as the principal products using PdCl 2 /tris(2-methoxyphenyl)phosphine. Only aromatic amines were used in these cases. , Later, Huang and co-workers developed a strategy to provide N -alkyl linear amides as the major products by using aminals or a combination of amine and paraformaldehyde as the amine sources .…”

Section: Introductionmentioning

confidence: 99%

Highly Ligand-Controlled Regioselective Pd-Catalyzed Aminocarbonylation of Styrenes with Aminophenols

2016

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Achieving chemo- and regioselectivity simultaneously is challenging in organic synthesis. Transition metal-catalyzed reactions are effective in addressing this problem by the diverse ligand effect on the catalyst center. Ligand-controlled regioselective Pd-catalyzed carbonylation of styrenes with aminophenols was realized, chemoselectively affording amides. Using a combination of boronic acid and 5-chlorosalicylic acid as the additives, linear amides were obtained in high yields and selectivity using tris(4-methoxyphenyl)phosphine (L3) in acetonitrile, while branched amides were obtained in high yields and selectivity in butanone by changing the ligand to 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phenyl-6-phosphaadamantane (L5). Further studies show that the nature of the ligand is key to the regioselectivity. Cone angle and Tolman electronic parameter (TEP) have been correlated to the reactivity and regioselectivity. Studies on the acid additives show that different acids act as the proton source and the corresponding counterion can help enhance the reactivity and selectivity.

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Palladium‐Catalyzed Aminocarbonylation of Aliphatic Alkenes with N,N‐Dimethylformamide as an In Situ Source of CO

Cited by 28 publications

References 61 publications

Magic of Alpha: The Chemistry of a Remarkable Bidentate Phosphine, 1,2-Bis(di-tert-butylphosphinomethyl)benzene

Magic of Alpha: The Chemistry of a Remarkable Bidentate Phosphine, 1,2-Bis(di-tert-butylphosphinomethyl)benzene

Direct Synthesis of Amides from Oxidative Coupling of Benzyl Alcohols or Benzylamines with N‐Substituted Formamides Using a Cu‐Fe‐Based Heterogeneous Catalyst

Highly Ligand-Controlled Regioselective Pd-Catalyzed Aminocarbonylation of Styrenes with Aminophenols

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