C-糖苷核糖酸及核糖醛的合成
收稿日期: 2016-02-01
修回日期: 2016-03-09
网络出版日期: 2016-03-18
基金资助
国家自然科学基金（Nos.21172051，21372059）资助项目.
Synthesis of C-Glycosides Ribosyl-Acid and Ribosyl-Aldehyde
Received date: 2016-02-01
Revised date: 2016-03-09
Online published: 2016-03-18
Supported by
Project supported by the National Natural Science Foundation of China (Nos. 21172051, 21372059).
为了探讨C-糖苷高效、简便的合成方法，分别以D-核糖和2，3-O-异丙叉基-D-核糖为原料，与膦叶立德进行Wittig-Michael加成串联反应，然后不同碱处理，一锅法高产率立体专一性地合成相应的（2，3-O-异丙叉基）-β-C-D-核糖乙酸乙酯和（2，3-O-异丙叉基）-β-C-D-核糖乙酸； 所得酯经DIBAL-H低温还原，得相应的核糖基醛衍生物； 以D-木糖为原料，经1，2-羟基保护成缩丙酮，3，5-位二羟基三氟甲磺酰基化、叠氮化，1，2-羟基脱保护，然后经与膦叶立德Wittig-Michael加成串联反应，碱处理，高产率、立体专一性地合成了含两个叠氮基的β-C-D-核糖乙酸. 提供了一种C-糖苷及氨基C-糖苷快捷、高效、简便的合成方法. 化合物结构经1H NMR、13C NMR、HRMS等确证.
关键词： 碳苷; Wittig-Michael加成; 糖酸; 糖醛; 叠氮化合物
张平竹 , 刘欢 , 魏笑 , 马趁 , 王齐伟 , 李小六 . C-糖苷核糖酸及核糖醛的合成[J]. 有机化学, 2016 , 36(7) : 1690 -1695 . DOI: 10.6023/cjoc201602003
For exploring a simple and efficient synthetic method of C-glycosides, (2,3-O-isopropylidene)-β-C-D-ribosyl ethyl acetate and (2,3-O-isopropylidene)-β-C-D-ribosyl acetic acid were stereospecifically synthesized by a one-pot tandem Wittig-Michael addition reaction, and then treated with corresponding base, respectively. The acetates were reduced by DIBAL-H to obtain the corresponding glycosyl aldehyde. D-xylose was treated following the procedure of acetonide of 1,2-position, trifluoroacetoxyation of 3,5-position. The trifluoroacetoxyl groups were substituted by azido groups, followed by the one-pot tandem Wittig-Michael addition reaction, and then treated with corresponding base. 3,5-Diazido-β-C-D-ribosyl acetic acid was obtained in high stereo specificity.
Key words： C-glycosides; Wittig-Michael addition; ribosyl-acid; aldehyde; azides
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