ABSTRACT
A one-step synthesis of cytotoxic 2-aroylpyrimidines by the denitrogenative reaction of 1-tosyl-1,2,3-triazoles with isoxazoles under rhodium catalysis has been developed. According to the density functional theory calculations and control experiments, the disclosed reaction proceeds via the rearrangement of an oxadiazatetraene intermediate involving a cascade of intramolecular aza-Diels-Alder and retro-aza-Diels-Alder reactions. The presence of a substituent at C4 of the isoxazole is a prerequisite for the formation of the pyrimidines.
ABSTRACT
1,4,8-Triazaocta-1,3,5,7-tetraenes, generated in situ by Rh2(Piv)4-catalyzed denitrogenative coupling of pyrazoles with 1-sulfonyl-1,2,3-triazoles, smoothly form 2,6,8-triazabicyclo[3.2.1]octa-3,6-dienes via intramolecular aza-Diels-Alder cycloaddition. This domino reaction, combined with the subsequent thermal or acid-catalyzed rearrangement of the cycloadducts, provides direct and flexible access to N-sulfonylated (Z)-2-(2-aminovinyl)imidazoles.
ABSTRACT
An effective method for the synthesis of fully substituted 5-sulfonamidoimidazoles by Rh(II)-catalyzed transannulation of 1,2,4-oxadiazole derivatives with N-sulfonyl-1,2,3-triazoles is reported. The reaction works well with both aromatic 1,2,4-oxadiazoles and 1,2,4-oxadiazol-5-ones providing a flexible approach to N-(alkoxy/amino)carbonyl- and N-alkyl-substituted imidazoles. Both the disclosed reactions are completely regioselective and provide the first examples of a carbenoid-mediated transformation of N,N,O-heterocycles.
