Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base...Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base attacked at the carbon of 1,2-O-methylidene moiety instead of anomeric carbon of ribose was observed and the structure of products 5a, 5b were identified by NMR and X-Ray diffraction.展开更多
1-O-methyl-3,5-2-O-(2,4-dichlorobenzyl)-D-ribofuranose-2-tone was produced by oxidizing 1-O-methyl-3,5-bis-O-(2,4-dichlorobenzyl)-D-ribofuranose,which was synthesized from hydroxyl protection and selectively removing ...1-O-methyl-3,5-2-O-(2,4-dichlorobenzyl)-D-ribofuranose-2-tone was produced by oxidizing 1-O-methyl-3,5-bis-O-(2,4-dichlorobenzyl)-D-ribofuranose,which was synthesized from hydroxyl protection and selectively removing O-2-protection of D-ribofuranose.Three oxidation methods,PDC,DMP and Albright-Goldman were studied in the paper.It was revealed that post-processing of PDC was harder to achieve with lots of by-products,at a yield of 39.6%.The DMP method was not suitable for industrialization due to the high cost,though the yield was as high as 91.8%.The Albright-Goldman method was the suitable oxidation method for the post-processing with its 52.0% yield.The product was characterized by MS,IR and 1HNMR.展开更多
基金This work was supported by the National Natural Science Foundation of China.
文摘Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base attacked at the carbon of 1,2-O-methylidene moiety instead of anomeric carbon of ribose was observed and the structure of products 5a, 5b were identified by NMR and X-Ray diffraction.
文摘1-O-methyl-3,5-2-O-(2,4-dichlorobenzyl)-D-ribofuranose-2-tone was produced by oxidizing 1-O-methyl-3,5-bis-O-(2,4-dichlorobenzyl)-D-ribofuranose,which was synthesized from hydroxyl protection and selectively removing O-2-protection of D-ribofuranose.Three oxidation methods,PDC,DMP and Albright-Goldman were studied in the paper.It was revealed that post-processing of PDC was harder to achieve with lots of by-products,at a yield of 39.6%.The DMP method was not suitable for industrialization due to the high cost,though the yield was as high as 91.8%.The Albright-Goldman method was the suitable oxidation method for the post-processing with its 52.0% yield.The product was characterized by MS,IR and 1HNMR.
