A facile approach to phosphonic acid diesters

Abstract

ABSTRACT:The symmetric H-phosphonates of carbohydrate and other compounds were conveniently prepared by direct transesterification of the corresponding monohydroxylic compounds with diphenyl phosphite. The approach has the merits of mild reaction conditions and high yields.

Multimetallic Pd- and Ni-catalyzed C(sp2)–P cross-coupling under aqueous micellar conditions

“…70 Dialkyl H -phosphonates can also be prepared by transesterification of diphenyl H -phosphonate ( 108 ). 71 In this process, 108 is mixed with an alcohol under basic (pyridine) and neat conditions, thereby completely avoiding corrosive PCl 3 . For this reason, we assessed whether commercial diphenyl H -phosphonate ( 108 ) can be used as an inexpensive ($0.50 per gram at Sigma-Aldrich) source of dialkyl H -phosphonates formed in situ and then directly, without isolation, converted into arylphosphonates in micellar C(sp 2 )–P cross-coupling, in a one-pot process.…”

Sulfurization of H-Phosphonate Diesters by Elemental Sulfur under Aqueous Conditions

“…The model H-phosphonate diester 1h was synthesized from 2′,3′- O -methyleneadenosine ( 2 ) following a procedure previously reported for various primary and secondary alcohols. 35 Accordingly, the phenoxo ligands of diphenyl phosphite were displaced by 2′,3′- O -methyleneadenosine ( 2 ) 36 in anhydrous pyridine (Scheme 2). The desired product 1h precipitated out of the reaction mixture and could be isolated by simple filtration.…”

“…The model H-phosphonate diester 1h was synthesized from 2′,3′-O-methyleneadenosine (2) following a procedure previously reported for various primary and secondary alcohols. 35 Accordingly, the phenoxo The desired product 1h precipitated out of the reaction mixture and could be isolated by simple filtration. The respective monoester 3h was obtained through a similar process except that an excess of diphenyl phosphite was used, and the transesterification step was followed by hydrolytic cleavage of any remaining phenoxo ligands (Scheme 2).…”

Characteristic fragmentation behavior of phosphoamino acid conjugates with 3′‐azido‐3′‐deoxythymidine by electrospray ionization tandem mass spectrometry

“…Phosphoamino acids are a kind of biologically interesting molecules and have been studied in detail in our laboratory 7. In our continuous study of novel bioconjugates to search for bioactive prodrugs,8–10 a series of phosphoamino acid conjugates with AZT was synthesized in a convenient way and their structures were determined on the basis of the spectral data. The characteristic fragmentation behavior of phosphoamino acid conjugates with 3′‐azido‐3′‐deoxythymidine will be presented in electrospray ionization tandem mass spectrometry.…”