Unusual reactions of diazocarbonyl compounds with α,β-unsaturated δ-amino esters: Rh(II)-catalyzed Wolff rearrangement and oxidative cleavage of N-H-insertion products.
Rh(II)-сatalyzed reactions of aroyldiazomethanes, diazoketoesters and diazodiketones with α,β-unsaturated δ-aminoesters, in contrast to reactions of diazomalonates and other diazoesters, give rise to the Wolff rearrangement and/or oxidative cleavage of the initially formed N-H-insertion products. These oxidation processes are mediated by Rh(II) catalysts possessing perfluorinated ligands. The formation of pyrrolidine structures, characteristic for catalytic reactions of diazoesters, was not observed in these processes at all.
Saint-Petersburg State University, Universitetskiy prosp. 26, St.-Petersburg 198504, Russia.
Valerij A
VA
Nikolaev
Saint-Petersburg State University, Universitetskiy prosp. 26, St.-Petersburg 198504, Russia.
Jury J
JJ
Medvedev
Saint-Petersburg State University, Universitetskiy prosp. 26, St.-Petersburg 198504, Russia.
Olesia S
OS
Galkina
Saint-Petersburg State University, Universitetskiy prosp. 26, St.-Petersburg 198504, Russia.
Ksenia V
KV
Azarova
Universität Leipzig, Institut für Organische Chemie, Johannisallee 29, D-04103 Leipzig, Germany.
Christoph
C
Schneider
N–H-insertion; Wolff rearrangement; diazo compounds; oxidation cleavage; transition-metal-catalyzed reactions