Addition of H-phosphonates to quinine-derived carbonyl compounds. An unexpected C9 phosphonate-phosphate rearrangement and tandem intramolecular piperidine elimination.
The Abramov reaction, a base-catalyzed nucleophilic addition of dialkyl H-phosphonates (phosphites) to carbonyl compounds, was performed with oxidized quinine derivatives as the substrates. Homologous aldehydes obtained from the vinyl group reacted in a typical way which led to α-hydroxyphosphonates, first reported compounds containing a direct P-C bond between the quinine carbon skeleton and a phosphorus atom. For the C9 ketones a phosphonate-phosphate rearrangement, associated with a tandem elimination of the piperidine fragment, was evidenced.
Department of Bioorganic Chemistry, Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
Lukasz
L
Górecki
Department of Bioorganic Chemistry, Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
Artur
A
Mucha
Department of Bioorganic Chemistry, Faculty of Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
Paweł
P
Kafarski
carbonyl derivatives; dialkyl phosphite addition; organophosporus; phosphonate–phosphate rearrangement; quinine oxidation