Copper-Catalyzed Multicomponent Coupling of Organoindium Reagents with Nitrogen-Containing Aromatic Heterocycles

• Published in: European Journal of Organic Chemistry Vol. 2010; no. 19; pp. 3650 - 3656
• Main Authors: Beveridge, Ramsay E., Black, Daniel A., Arndtsen, Bruce A.
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01-07-2010; WILEY‐VCH Verlag; Wiley-VCH
• Subjects: Chemistry; Copper; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with n hetero atom and also o and/or s, se, te hetero atoms; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Multicompo­nent reactions; Nitrogen heterocycles; Organic chemistry; Organo­indium reagents; Preparations and properties; Pyridinium salts; One pot reaction; Organoindium reagents; Organic cation; Mild operating conditions; Nitrogen heterocycle; Pyridine derivatives; Pyridinium compounds; Indium Organic compounds; Multicomponent reactions; Functionalization; Pyridinium salts; Aromatic compound; Oxidation; Chemical synthesis; Copper; Oxygen nitrogen heterocycle; Sulfur nitrogen heterocycle; Benzoxazole derivatives; Catalytic reaction; Chemical reagent; Multicomponent reaction; Transition metal; Benzothiazole derivatives; Phthalazine derivatives; Copper ion; Nitrogen heterocycles
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201000231

A mild, copper‐catalyzed coupling of organoindium reagents with nitrogen‐containing aromatic heterocycles and chloroformates is described. This reaction proceeds with a range of organoindium reagents, yielding predominately or exclusively the 1,4‐addition products with pyridine. In addition, a range of other nitrogen‐containing heterocycles can be employed in this reaction (e.g. benzoxazole, benzothiazole, phthalazine). As an illustration of the utility of this reaction, this heterocycle functionalization is coupled with a subsequent oxidation to achieve the one‐pot synthesis of functionalized pyridine and benzothiazole derivatives.
A copper‐catalyzed, multicomponent method to directly derivatize pyridine and other nitrogen‐containing heterocycles (e.g. benzoxazoles, benzothiazoles, phthalazines) is described. This provides a mild andone‐step approach to couple heterocycles with organoindium reagents without initial pre‐derivatization of the ring or the use of strong nucleophiles.