Nucleosides and Nucleotides. 232. Synthesis of 2′-C-Methyl-4′-thiocytidine: Unexpected Anomerization of the 2′-Keto-4′-thionucleoside Precursor

• Published in: Nucleosides, nucleotides & nucleic acids Vol. 24; no. 10-12; pp. 1789 - 1800
• Main Authors: Kaga, Daisuke, Minakawa, Noriaki, Matsuda, Akira
• Format: Journal Article
• Language: English
• Published: PHILADELPHIA Taylor & Francis Group 01.09.2005; Taylor & Francis
• Subjects: 2′-Branched- chain-4′-thionucleoside; 2′-C-methyl-4′-thiocytidine; 2′-Keto-4′-thionucleoside; 4′-Thionucleoside; Biochemistry & Molecular Biology; Cytidine - analogs & derivatives; Cytidine - chemical synthesis; Cytidine - chemistry; Life Sciences & Biomedicine; Nucleoside; Science & Technology; 2 '-branched- chain-4 '-thionucleoside; RADICAL DEOXYGENATION; DESIGN; 4 '-thionucleoside; MECHANISM; nucleoside; 2 '-C-methyl-4 '-thiocytidine; TERT-ALCOHOLS; 2 '-keto-4'-thionucleoside; SUGAR PYRIMIDINE NUCLEOSIDES; ANTITUMOR-ACTIVITY; 2'-DEOXY-2'-METHYLIDENECYTIDINE
• ISSN: 1525-7770; 1532-2335
• DOI: 10.1080/15257770500267204

The synthesis of 2′-C-methyl-4′-thiocytidine (16) is described. Since the 2′-keto-4′-thiocytidine derivative 2β unexpectedly isomerized to 2α and the methylation of 2β proceeded predominantly from the less hindered α-face to give 7, the desired product 16 was synthesized via the Pummerer reaction of the sulfoxide 14 and N 4 -benzoylcytosine.