Ueber eine neue Bildungsweise von Diphenylaminderivaten

Ullmann, Fritz

doi:10.1002/cber.190303602174

Cited by 864 publications

(389 citation statements)

References 2 publications

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“…However, results improved significantly in the presence of both Cu and Cu 2 O and 3 was produced in 71% and 76% after 5 and 24 hours, respectively (Table 1, entries 5 and 7). Variation of the Cu/Cu 2 O-ratio and replacement of Cu 2 O by CuI did not further increase yields (Table 1, entries 4,[6][7][8][9].…”

Section: Resultsmentioning

confidence: 99%

Regioselective Copper-Catalyzed Amination of Chlorobenzoic Acids: Synthesis and Solid-State Structures of N-Aryl Anthranilic Acid Derivatives

2005

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A chemo-and regioselective copper-catalyzed cross-coupling reaction for effective amination of 2-chlorobenzoic acids with aniline derivatives has been developed. The method eliminates the need for acid protection and produces a wide range of N-aryl anthranilic acid derivatives in up to 99%. The amination was found to proceed with both electron-rich and electron-deficient aryl chlorides and anilines and also utilizes sterically hindered anilines such as 2,6-dimethylaniline and 2-tertbutylaniline. The conformational isomerism of appropriately substituted N-aryl anthranilic acids has been investigated in the solid state. Crystallographic analysis of seven anthranilic acid derivatives showed formation of two distinct supramolecular architectures exhibiting trans-anti-and unprecedented trans-syn-dimeric structures.

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Section: Resultsmentioning

confidence: 99%

Regioselective Copper-Catalyzed Amination of Chlorobenzoic Acids: Synthesis and Solid-State Structures of N-Aryl Anthranilic Acid Derivatives

2005

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“…17 The Ullmann ether synthesis is a reaction, in which a phenol is coupled to an aryl halide to create a diaryl ether in the presence of a copper compound. [18][19][20] Recently, it was found that addition of relatively cheap ligands (diamines, aminoalcohols, diketones, diols) made this reaction catalytic. Progress has been made by combination of mili-scale processing and microwave heating for the Cu-catalyzed Ullmann etherification in chemical synthesis, providing improved catalytic activity.…”

Section: Overview Of Traditional and Less Known Methodsmentioning

confidence: 99%

Ethers from esters; from exceptional transformation to synthetic method

Jakopović¹,

Kapić²,

Alihodžić³

et al. 2015

Arkivoc

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Most ether-bond forming reactions based on traditional methods or modifications thereof require strongly acidic or basic conditions and often harsh reaction conditions. Reduction of esters to ethers has been regarded as an impracticable method, generally affording alcohols as the principal products. Only recently, original, mostly catalytic methods for reduction of esters to ethers have been reported, which proceed under mild conditions and are compatible with many functional groups present in the substrate ester molecule. These reactions are considered as a valuable alternative to traditional methods, and specific protocols have been reported. An account of the progress in this synthetic methodology is given.

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“…Despite its undoubtedly current success, after the seminal work by Fritz Ullmann [7][8][9] and Iram Goldberg [10] in the early 20th century, these reactions did not garner considerable attention from the synthetic community. This was a consequence of the harsh reaction condition requirements such as stoichiometric amounts of copper, strong bases, high temperatures, and long reaction times [11].…”

Section: Introductionmentioning

confidence: 99%

Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

et al. 2017

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Density Functional Theory (DFT) calculations have been carried out in order to unravel the governing reaction mechanism in copper-catalyzed cross-coupling Ullmann type reactions between iodobenzene (1, PhI) and aniline (2-NH, PhNH 2 ), phenol (2-O, PhOH) and thiophenol (2-S, PhSH) with phenanthroline (phen) as the ancillary ligand. Four different pathways for the mechanism were considered namely Oxidative Addition-Reductive Elimination (OA-RE), σ-bond Metathesis (MET), Single Electron Transfer (SET), and Halogen Atom Transfer (HAT). Our results suggest that the OA-RE route, involving Cu III intermediates, is the energetically most favorable pathway for all the systems considered. Interestingly, the rate-determining step is the oxidative addition of the phenyl iodide to the metal center regardless of the nature of the heteroatom. The computed energy barriers in OA increase in the order O < S < NH. Using the Activation Strain Model (ASM) of chemical reactivity, it was found that the strain energy associated with the bending of the copper(I) complex controls the observed reactivity.

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Ueber eine neue Bildungsweise von Diphenylaminderivaten

Cited by 864 publications

References 2 publications

Regioselective Copper-Catalyzed Amination of Chlorobenzoic Acids: Synthesis and Solid-State Structures of N-Aryl Anthranilic Acid Derivatives

Regioselective Copper-Catalyzed Amination of Chlorobenzoic Acids: Synthesis and Solid-State Structures of N-Aryl Anthranilic Acid Derivatives

Ethers from esters; from exceptional transformation to synthetic method

Understanding the Heteroatom Effect on the Ullmann Copper-Catalyzed Cross-Coupling of X-Arylation (X = NH, O, S) Mechanism

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