Jacek Stawinski

Nucleoside H-phosphonates. III. Chemical synthesis of oligodeoxyribonucleotides by the hydrogenphosphonate approach

Abstract A rapid synthesis of oligodeoxyribonucleotides on solid support is described via coupling of the deoxyribonucleoside 3′- H-phosphonates in the presence of various condensing reagents.

Microwave-Assisted Palladium-Catalyzed Cross-Coupling of Aryl and Vinyl Halides with H-Phosphonate Diesters

A general and efficient method for the microwave-assisted formation of the C-P bond was developed. Using a prevalent palladium catalyst, Pd(PPh3)4, a quantitative cross-coupling of various H-phosphonate diesters with aryl and vinyl halides was achieved in less than 10 min. The reactions occurred with retention of configuration at the phosphorus center and in the vinyl moiety. Using this protocol, several C-phosphonates, including those bearing nucleoside and cholesteryl moieties, were prepared in high yields.

Nucleoside H-phosphonates. IV. Automated solid phase synthesis of oligoribonucleotides by the hydrogenphosphonate approach

Abstract A rapid and efficient synthesis of oligoribonucleotides on solid support is described via coupling of 5′- O -dimethoxytrityl-2′- O -t-butyldimethylsilyl ribonucleoside 3′-H-phosphonates II to the polymer bound nucleoside in the presence of pivaloyl chloride as coupling agent.

Studies on aryl H-phosphonates. I: An efficient method for the preparation of deoxyribo- and ribonucleoside 3'-H-phosphonate monoesters by transesterification of diphenyl H-phosphonate

Abstract A convenient method for the preparation of deoxyribonucleoside and ribonucleoside 3′-H-phosphonate monoesters via transesterification of diphenyl H-phosphonate with suitable protected nucleosides in pyridine is described.

H-Phosphonates: Versatile synthetic precursors to biologically active phosphorus compounds*

In this review, a short account of H-phosphonate chemistry and its application to the synthesis of biologically important phosphates and their analogs is given.

Nucleoside H-phosphonates. X: Studies on nucleoside hydrogenphosphonothioate diester synthesis

Abstract Synthesis and chemical properties of nucleoside H-phosphonothioates are discussed in the context of possible application of these compounds as intermediates in the synthesis of oligonucleotide analogues.

Nucleoside H-Phosphonates. V. The Mechanism of Hydrogenphosphonate Diester Formation Using Acyl Chlorides as Coupling Agents in Oligonucleotide Synthesis by the Hydrogenphosphonate Approach

The H-phosphono-acyl mixed anhydrides of type III were found to be the main intermediates during H-phosphonate diester formation using acyl chlorides as coupling agents in the reaction of hydrogenp...

Palladium-Catalyzed Propargylic Substitution with Phosphorus Nucleophiles: Efficient, Stereoselective Synthesis of Allenylphosphonates and Related Compounds

A new, efficient method is developed, based on a palladium(0)-catalyzed reaction of propargylic derivatives with various phosphorus nucleophiles, to produce allenylphosphonates and their analogues with defined stereochemistry in the allenic and the phosphonate moiety.

Nucleoside H-Phosphonates. XI. A Convenient Method for the Preparation of Nucleoside H-Phosphonates

Abstract A simple synthetic method for the preparation of nucleoside 3′-H-phosphonates, consisting of reaction of suitably protected nucleosides with phosphonic acid in the presence of a condensing agent, has been developed.

Studies on aryl H-phosphonates. 3. Mechanistic investigations related to the disproportionation of diphenyl H-phosphonate under anhydrous basic conditions

Abstract Diphenyl H-phosphonate undergoes under anhydrous reaction conditions a base-promoted disproportionation to triphenyl phosphite and phenyl H-phosphonate. On the basis of 31P NMR data the most likely mechanism for this transformation was proposed. In order to substantiate these findings and to get a deeper insight into the chemistry of aryl H-phosphonate esters, we carried out also some studies on activation of phenyl and diphenyl H-phosphonates with various condensing agents. We found that aryl vs alkyl esters of phosphonic acid often follow different reaction pathways during the activation, and this can most likely be traced back to higher electrophilicity of the phosphorus centre and to higher reactivity of the P-H bonds in aryl H-phosphonate derivatives.