化学
尿嘧啶
立体选择性
戒指(化学)
蒂奥-
吡啶
另一个
立体化学
衍生工具(金融)
产量(工程)
药物化学
有机化学
冶金
材料科学
DNA
经济
催化作用
金融经济学
生物化学
作者
Kazuhiro Haraguchi,Noyori Hannda,Mizuki Wakasugi,Madoka Maruyama,Hirokazu Ishii,Daisuke Nagano,Hiroyuki Kumamoto
出处
期刊:Synthesis
[Georg Thieme Verlag KG]
日期:2022-09-23
卷期号:54 (24): 5509-5519
标识
DOI:10.1055/s-0040-1720042
摘要
Abstract The unprecedented DAST-mediated (DAST = diethylaminosulfur trifluoride) deoxygenative fluorination of benzoyl-, TBDPS-, and Bn-protected 1-(β-d-4-thioarabinofuranosyl)uracil at the sugar portion was examined. Three kinds of nucleoside (Ns) products were formed: target thiolane Ns, ring-contracted thietane Ns, and anhydro Ns products. The reaction pathway was determined by the electronic effect of the protecting groups at the sugar and base moieties. The benzoylated uracil starting material gave the 2,2′-anhydronucleoside (anhydro Ns) as a major product, whereas the silylated and benzylated starting materials furnished the corresponding fluorinated products, in which the ring-contracted thietanes predominantly formed. The desired thiolane Ns could be obtained as major product by the addition of a pyridine derivative as an additive. Upon reacting N 3-benzoylated 1-(β-d-4-thioarabinofuranosyl)uracil with DAST in the presence of 2,4,6-collidine, the target 2′-deoxy-2′-β-fluoro-4′-thiouracil nucleoside could be obtained in 72% isolated yield along with the corresponding thietane Ns (7%) and anhydro Ns (3%) (thiolane Ns/thietane Ns/anhydro Ns = 10.3:1.00:0.43), with recovery of the starting material (12%). In this study, the first stereoselective synthesis of the β-anomer of 1-(2-deoxy-2-fluoro-4-thio-β-d-arabino-pentofuranosyl)cytosine (4′-thioFAC) has been developed.
科研通智能强力驱动
Strongly Powered by AbleSci AI