93403-76-0Relevant academic research and scientific papers
STUDIES ON THE REACTION OF NUCLEOSIDE PHOSPHORODIESTERS WITH ARYL SULFONYL CHLORIDES
Garegg, Per J.,Regberg, Tor,Stawinski, Jacek,Stroemberg, Roger
, p. 2665 - 2666 (1986)
It was found that activation of phosphorodiesters by aryl sulfonyl chlorides does not stop at the stage of symmetrical pyrophosphates I but proceeds further with the formation of diester chlorophosphates II.
31P NMR Study of the Mechanism of Activation and Coupling Reactions in the Synthesis of Oligodeoxyribonucleotides by the Phosphotriester Method
Chandrasegaran, Srinivasan,Murakami, Akira,Kan, Lou-sing
, p. 4951 - 4957 (2007/10/02)
The phosphotriester method provides a rapid and convenient procedure for synthesizing oligonucleotides.The mechanism has been revealed and intermediates have been identified by 31P NMR methodology.It was found that reaction of a 5'-protected nucleoside 3'-(p-chlorophenyl phosphate) with mesitylenesulfonyl chloride (MSCl) or 1-(mesitylyl-2-sulfonyl)-3-nitro-1,2,4-triazole (MSNT) in anhydrous pyridine yields only two products within 5 min, the sulfonic acid-phosphate mixed anhydride 2 and the (3'-3') symmetrical pyrophosphate tetraester 3 which can be isolated as a mixture.Reaction of 2 and 3 with 3'-O-acetylthymidine yields the phosphotriester dimer NpTOAc.The reaction rate and yield of dimers are closely dependent on the presence of catalysts.The reaction finished within minutes when tetrazole or 3-nitro-1,2,4-triazole was used.On the contrary, the reaction completed in hours when imidazole or 1,2,4-triazole was used as catalysts.The possible mechanisms are explored and discussed in detail.
