Ullmann-type amination

We synthesized uniform CU2O coated Cu nanoparticles from the thermal decomposition of copper acetylacetonate, followed by air oxidation. We successfully used these nanoparticles for the catalysts for Ullmann type amination coupling reactions of aryl chlorides. We synthesized core/shell-like Ni/Pd bimetallic nanoparticles from the consecutive thermal decomposition of metal-surfactant complexes. The nanoparticle catalyst was atom-economically applied for various Sonogashira coupling reactions. 

Synthesis of CU2O coated Cu nanoparticles and their successful applications to Ullmann-type amination coupling reactions of aryl chlorides... 

Scheme 3. Ullmann-type amination coupling reaction...

In the 1990s, a breakthrough was independently accomplished by Buchwald [105] (Scheme 1.31) and Hartwig [106] (Scheme 1.32), establishing broadly appU-cable palladium-catalyzed Ullmann-type aminations of haloarenes, employing amines directly as nucleophiles. Thereby, the preparation and use of tin amides could be circumvented, and intramolecular [105] aminations of haloarenes were shown also to occur efficiently. 

Uk Son, S., K501 Park, I., Park,)., and Hyeon, T. (2004) Synthesis of CU2O coated Cu nanoparticles and their successful applications to Ullmann-type amination coupling reactions of aryl chlorides, Chem. Common., 7, 778-779,... 

T3506). Similarly, 2-halobenzaldehydes, isonitriles, amines, and propar-gylic acids underwent Ugi reaction, then copper(I)-catalyzed alkyne—azide 1,3-dipolar cycloaddition, and then intramolecular Ullmann-type triazole N-arylation to afford triazolo-flised benzodiazepines such as 136 (13EJ01223). Similar reactions involving a post-Ugi lactamization or a post-Ugi intramolecular imination process delivered benzo-l,4-diazepin-2,5-dione derivatives or 4,5-dihydro-3H-l,4-benzodiazepine derivatives (13ACO202,13T9056). 

It should also be noted that copper-catalyzed Ullmann-type coupling of aryl halides with amines yields substituted products [206], and reaction with diphenylamine has been used to form triaryl-amines [207], Triarylamines may also be formed in a variation of the Meyers reaction [47] by displacement by lithium amides of fluoro- or methoxy-substituents activated by an ort/io-ester function [208], The oxidation of a-adducts is discussed in Chapter 11, but it should also be mentioned that aminated products may also be produced by the oxidation of adducts formed by the addition of amide or alkylamide ions at ring carbon atoms carrying hydrogen [209]. 

Other important anthraquinone vat dyes belong to the family known as indanthrones. Important examples of this structural type are C.I. Vat Blue 4 and Vat Blue 6. Vat Blue 4 is made by heating 1-amino or 2-aminoan-thraquinone at 220-230°C in a K0H/H20 mixture. The Vat Blue 6 synthesis is a much longer process that requires the synthesis of 2-chloro-3-aminoanthraquinone.57 The resultant amine is brominated and converted to the target dye via an Ullmann reaction. 

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