新型2',3'-二脱氢-2',3'-二脱氧-4'-硒代核苷的立体选择性合成及构象研究

Stereoselective synthesis and conformational study of novel 2',3'-Didehydro-2',3'-dideoxy-4'-selenonucleosides.

作者信息

Tosh Dilip K, Choi Won Jun, Kim Hea Ok, Lee Yoonji, Pal Shantanu, Hou Xiyan, Choi Jungwon, Choi Sun, Jeong Lak Shin

机构信息

Laboratory of Medicinal Chemistry, College of Pharmacy, Ewha Womans University, Seoul, Korea.

出版信息

J Org Chem. 2008 Jun 6;73(11):4259-62. doi: 10.1021/jo8003277. Epub 2008 May 3.

DOI:10.1021/jo8003277

PMID:18454552

Abstract

Stereoselective synthesis of novel 2',3'-didehydro-2',3'-dideoxy-4'-selenonucleosides (4'-seleno-d4Ns) 4a- c was accomplished via 4'-selenoribofuranosyl pyrimidines 11a- c, as key intermediates. 4'-Selenoribofuranosyl pyrimidines 11a- c were efficiently synthesized from d-ribose or d-gulonic gamma-lactone using a Pummerer-type condensation as a key step. Introduction of 2',3'-double bond was achieved by treating cyclic 2',3'-thiocarbonate with 1,3-dimethyl-2-phenyl-1,3,2-diazaphospholidine.

摘要

通过关键中间体4'-硒代呋喃核糖基嘧啶11a - c完成了新型2',3'-二脱氢-2',3'-二脱氧-4'-硒代核苷（4'-硒代-d4N）4a - c的立体选择性合成。4'-硒代呋喃核糖基嘧啶11a - c以d-核糖或d-古洛糖酸γ-内酯为原料，采用Pummerer型缩合作为关键步骤高效合成。通过用1,3-二甲基-2-苯基-1,3,2-二氮杂磷环戊烷处理环状2',3'-硫代碳酸酯实现2',3'-双键的引入。