NEW APPROACHES TO SYNTHESIS OF 3-DEOXY-3-FLUORO-D-GLUCOSE
NEW APPROACHES TO SYNTHESIS OF 3-DEOXY-3-FLUORO-D-GLUCOSE
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DOI：
10.1021/jo00400a014
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发表时间：
1978-01-01
影响因子：
3.6
通讯作者：
WELCH, MJ
中科院分区：
文献类型：
--
作者：
TEWSON, TJ;WELCH, MJ
二亚异丙基己糖衍生物1，2：5，6-二-O-亚异丙基-α- D-呋喃葡糖（1）和1，2：5，6-二-O-异亚丙基-α- D-呋喃阿洛糖（4）与二乙氨基三氟化硫（DAST）反应生成稳定但不稳定的中间体，该中间体可在硫原子上而不是在硫原子上进行进一步的亲核攻击。蒸馏1和DAST的反应混合物得到3-脱氧-1，2：5，6-二-O-异亚丙基-α- D-葡糖-己-3-烯呋喃糖，而5 [4和DAST之间反应的中间体]和DAST得到3-脱氧-3-氟-1，2：5，6-二-O-异亚丙基-α- D-呋喃葡萄糖（6）。通过放射性同位素18F的标记实验，6的形成被证明是SN 2置换。在快速和简单的反应中，6也可以由5的三氟甲磺酸酯和氟化铯制备。
The diisopropylidene hexose derivatives 1,2:5,6-di-O-isopropylidene-.alpha.-D-glucofuranose (1) and 1,2:5,6-di-O-isopropylidene-.alpha.-D-allofuranose (4) react with diethylaminosulfur trifluoride (DAST) to give stable but labile intermediates which can undergo further nucleophilic attack at sulfur rather than fluorination. Distillation of the reaction mixtures of 1 and DAST gives 3-deoxy-1,2:5,6-di-O-isopropylidene-.alpha.-D-gluco-hex-3-enofuranose, while 5 [an intermediate in the reaction between 4 and DAST] and DAST gave 3-deoxy-3-fluoro-1,2:5,6-di-O-isopropylidene-.alpha.-D-glucofuranose (6). The formation of 6 is shown to be an SN2 displacement by labeling experiments with the radioisotope 18F. In a rapid and simple reaction, 6 can also be prepared from the trifluoromethanesulfonate of 5 and cesium fluoride.