title: A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues.
abstract: A convenient approach has been developed to α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues by α-phosphonylation, α-phosphinylation or α-phosphinoylation of 1-(N-acylamino)alkylphosphonates, that, in turn, are easily accessible from N-acyl-α-amino acids. Effective electrophilic activation of the α-position of 1-(N-acetylamino)alkylphosphonates was achieved by electrochemical α-methoxylation of these compounds in methanol, mediated with NaCl, followed by displacement of the methoxy group with triphenylphosphonium tetrafluoroborate to give hitherto unknown 1-(N-acetylamino)-1-triphenylphosphoniumalkylphosphonate tetrafluoroborates. The latter compounds react smoothly with trialkyl phosphites, dialkyl phosphonites or alkyl phosphinites in the presence of Hünig's base and methyltriphenylphosphonium iodide in a Michaelis-Arbuzov-like reaction to give the expected alkylidenebisphosphonates, 1-phosphinylalkylphosphonates or 1-phosphinoylalkylphosphonates, respectively, in good yields.
authors.affiliation: Department of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, Poland.
authors.forename: Anna
authors.initials: A
authors.lastname: Kuźnik
authors.affiliation: Department of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, Poland.
authors.forename: Roman
authors.initials: R
authors.lastname: Mazurkiewicz
authors.affiliation: Department of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, Poland.
authors.forename: Mirosława
authors.initials: M
authors.lastname: Grymel
authors.affiliation: Department of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, Poland.
authors.forename: Katarzyna
authors.initials: K
authors.lastname: Zielińska
authors.affiliation: Department of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, Poland.
authors.forename: Jakub
authors.initials: J
authors.lastname: Adamek
authors.affiliation: Department of Bioorganic Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
authors.forename: Ewa
authors.initials: E
authors.lastname: Chmielewska
authors.affiliation: Department of Bioorganic Chemistry, Wrocław University of Technology, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław, Poland.
authors.forename: Marta
authors.initials: M
authors.lastname: Bochno
authors.affiliation: Department of Organic Chemistry, Biochemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, Poland.
authors.forename: Sonia
authors.initials: S
authors.lastname: Kubica
keywords: 1-phosphinoylalkylphosphonate; 1-phosphinylalkylphosphonate; alkylidenebisphosphonate; electrochemical α-methoxylation; α-amino acid phosphorus analogues