64364-95-0Relevant academic research and scientific papers
Large-scale synthesis of a key catalytic reagent for phosphorus protection in building blocks for isopolar phosphonate oligonucleotide preparation
Rejman, Dominik,Erbs, Jiri,Rosenberg, Ivan
, p. 473 - 476 (2013/08/07)
A simple procedure for the large-scale synthesis of 4-methoxy-2-pyridinemethanol 1-oxide (5), a key compound in modern triester synthesis of oligonucleotides, employing Buechi R 152 evaporator as a reaction apparatus was elaborated. Two crucial reaction steps, both strongly exothermic, were satisfactorily handled. Our procedure provides a high-purity, light-and heat-stable product in a satisfactory yield.
Protecting Groups in Nucleosides and Nucleotides Synthesis. VIII. Synthesis of (4-Substituted 2-Picolyl 1-Oxide)halides and 2'- and 3'-O-(4-Substituted-2-picolyl 1-Oxide)nucleosides
Mizuno, Yoshihisa,Endo, Takeshi,Takahashi, Akira,Inaki, Atsuko
, p. 3041 - 3048 (2007/10/02)
A number of alkylating agents of the 4-substituted pyridine N-oxide series, such as (4-nitro-, 4-methylthio-, or 4-methoxy-2-picolyl 1-oxide)halide, have been prepared.Treatment of 2',3'-O-(dibutylstannylene)uridine or 2',3'-O-(dibutylstannylene)adenosine with the alkylating agents afforded the corresponding 2'-O- and 3'-O-(4-substituted 2-picolyl 1-oxide)nucleosides. 2'-O-(4-Nitro-2-picolyl 1-oxide)uridine was converted to the 4-methoxy-2-picolyl derivative on treatment with methanolic sodium methoxide at 60 deg C.However, it was found that the treatment of adenosine with sodium hydride in DMF, followed by alkylation with (4-methoxy-2-picolyl 1-oxide)chloride gave a more satisfactory yield (56.4percent) of 2'-O-(4-methoxy-2-picolyl 1-oxide)adenosine. 2'-O-(4-Methylthio-2-picolyl 1-oxide)adenosine could be similarly prepared in 36.7percent yield. 4-Methoxy-2-picolyl protection was removable under milder conditions than 2-picolyl 1-oxide protection.Phosphorylation of 17 with phosphoryl chloride in triethyl phosphate gave the corresponding 5'-phosphate in 57.8percent yield.Keywords - 4-substituted 2-picolyl 1-oxide; protecting group in nucleotide synthesis; acetic anhydride rearrangement of α-picolyl 1-oxide; 2'-O-substituted adenosine; 2'-O-substituted uridine; 4-methoxy-2-pyridyl carbinol 1-oxide; 4-methylthio-2-pyridyl carbinol 1-oxide; 4-nitro-2-pyridyl carbinol 1-oxide.
