α‐Substituierte Phosphonate. 39. Methandiphosphonsäureester durch UV‐induzierte Michaelis‐Becker‐Reaktion

Abstract

α‐Substituted Phosphonates. 39. Methane‐diphosphonic Esters by U.V.‐Induced Michaelis‐Becker‐Reaction Dibromomethane resp. chlorbromomethane reacts with sodium dialkyl phosphite in heptane‐/liq.NH3 or in liq. NH3 by u.v. irradiation at low temperatures to give in good yields methane diphosphonic acid tetraalkylesters 1. In the same manner with sodium diethyl thionophosphite the corresponding methane‐bis‐thiophosphonic acid tetraethylester 4 is obtained.

Synthesis of Enzymatically and Chemically Non-hydrolyzable Analogues of Dinucleoside Triphosphates Ap3A and Gp3G

“…Many strategies have been developed for the synthesis of methylene analogues of diphosphate; − however, only a very small number have been directed toward the preparation of bis-methylene analogues of triphosphate. − The latter are exclusively based on a double Michaelis−Arbuzov reaction between a bis-chloromethylphosphinate and a phosphorus triester (Scheme ). The introduction of one or two nucleoside moieties into the polyphosphate analogue backbone ,, requires the saponification of all 5-alkyl esters prior to coupling, since the partial regioselective hydrolysis of these compounds is expected to be very difficult and has not been previously described.…”

“…Many strategies have been developed for the synthesis of methylene analogues of diphosphate; [24][25][26][27][28][29][30][31][32][33][34] however, only a very small number have been directed toward the preparation of bis-methylene analogues of triphosphate. [35][36][37][38] The latter are exclusively based on a double Michaelis-Arbuzov reaction between a bis-chloromethylphosphinate and a phosphorus triester (Scheme 2).…”