methyl 3-chloro-β-D-3-deoxy-allopyranoside | 4991-00-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-chloro-β-D-3-deoxy-allopyranoside
• 英文别名: (2R,3R,4R,5S,6R)-4-chloro-2-(hydroxymethyl)-6-methoxyoxane-3,5-diol
• CAS: 4991-00-8
• 化学式: C₇H₁₃ClO₅
• 分子量: 212.63
• InChiKey: NBTWAGXIQGULSL-NYMZXIIRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.8
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  79.2
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 3-chloro-β-D-3-deoxy-allopyranoside 在 硫酸 作用下， 生成 3-chloro-D-3-deoxy-allose
  参考文献：
  名称：

  糖氯硫酸盐的反应：第五部分。氯脱氧糖的合成

  摘要：

  磺酰氯与还原糖和它们的甲基吡喃糖苷的反应显示产生含有氯脱氧和氯硫酸酯基团的完全取代的吡喃糖衍生物。结果表明，氯代脱氧基团是通过完全氯硫酸化中间体中特定反应性氯硫酸根基团的氯离子通过亲核置换 (SN2) 形成的。显示氯取代的程度由单个吡喃糖衍生物中的空间和电子效应决定。

  DOI：

  10.1139/v65-319
• 作为产物：
  描述：

  甲基 4,6-O-亚苄基-β-D-吡喃葡萄糖苷 在 吡啶 、 盐酸 、 四氯化碳 、 三苯基膦 作用下， 以 甲醇 为溶剂， 反应 6.0h， 生成 methyl 3-chloro-β-D-3-deoxy-allopyranoside
  参考文献：
  名称：

  Halogenation reactions of derivatives ofd-glucose and sucrose

  摘要：

  Treatment of methyl 4,6-O-benzylidene-alpha-D-glucopyranoside (1) with triphenylphophine-carbon tetrachloride-pyridine (reagent A) gave methyl 4,6-O-benzylidene-2-chloro-2-deoxy-alpha-D-mannopyranoside (2). When reagent A was used in excess, a further elimination reaction occurred to give methyl 4,6-O-benzylidene-2-chloro- (6, 60%) and -3-chloro-2,3-dideoxy-alpha-D-erythro-hex-2-enopyranoside (7, 16%). Treatment of 1 with triphenylphosphine-carbon tetrabromide-pyridine (reagent B) caused little or no elimination, and 47% of methyl 4,6-O-benzylidene-2-bromo-2-deoxy-alpha-D-mannopyranoside (14) was obtained. On treatment with reagent A, methyl alpha-D-glucopyranoside (16) gave exclusively methyl 2,4,6-trichloro- 2,3,4,6-tetradeoxy-alpha-D-erythro-hex-2-enopyranoside (17), and methyl 4,6-O-benzylidene-beta-D-glucopyranoside (19) gave methyl 4,6-O-benzylidene-3-chloro-3-deoxy-beta-D-allopyranoside (20, 70%). However, with reagent B, 19 gave methyl 4,6-O-benzylidene-3-bromo-3-deoxy-beta-D-glucopyranoside (23, 66%), probably by way of double inversion of configuration at C-3. Likewise, with reagent A, methyl beta-D-glucopyranoside (25) gave methyl 2,4,6-trichloro- (26) and3,4,6-trichloro-2,3,4,-6-tetradeoxy- beta-D-threo-hex-2-enopyranoside (27), and 4,6-O-isopropylidenesucrose (28) gave mainly 3-chloro-3-deoxy-4,6-O-isopropylidene-alpha-D-allopyranosyl 1,4,6-trichloro-1,4,6-trideoxy-beta-D-lyxo-hexulofuranoside (29) together with 3-chloro-3-deoxy-4,6-O-isopropylidene-alpha-D-allopyranosyl 1,4,6-trichloro-1,4,6-trideoxy-beta-D-fructofuranoside (30). The assignment of structure to 29 is tentative.

  DOI：

  10.1016/0008-6215(90)80141-o

文献信息

• Site-Selective Dehydroxy-Chlorination of Secondary Alcohols in Unprotected Glycosides
  作者：Ji Zhang、Niels R. M. Reintjens、Jayaraman Dhineshkumar、Martin D. Witte、Adriaan J. Minnaard

  DOI：10.1021/acs.orglett.2c01992

  日期：2022.7.29

  To circumvent protecting groups, the site-selective modification of unprotected glycosides is intensively studied. We show that site-selective oxidation, followed by treatment of the corresponding trityl hydrazone with tert-butyl hypochlorite and a H atom donor provides an effective way to introduce a chloride substituent in a variety of mono- and disaccharides. The stereoselectivity can be steered

  为了规避保护基团，对未受保护的糖苷的位点选择性修饰进行了深入研究。我们表明，位点选择性氧化，然后用次氯酸叔丁酯和 H 原子供体处理相应的三苯甲基腙，提供了一种在各种单糖和二糖中引入氯化物取代基的有效方法。立体选择性是可以控制的，并且还描述了一种新的孪生二氯化反应。这一策略挑战了导致过度氯化的现有方法。
• Site-selective introduction of thiols in unprotected glycosides
  作者：Niels R. M. Reintjens、Martin D. Witte、Adriaan J. Minnaard

  DOI：10.1039/d3ob00817g

  日期：——

  converted into a thiol moiety. The transformation involves SN1-substitution of a chloro-azo intermediate, formed by oxidation of the corresponding trityl hydrazone, with a thiol. The prepared deoxythio sugars provide, in combination with the recently developed protecting group-free glycosylation of glycosyl fluorides, a protecting group-free synthesis of thioglycosides.

  硫代糖苷或S-连接糖苷是重要的糖模拟物。这些硫代糖苷通常通过糖基化脱氧硫代糖受体来制备，脱氧硫代糖受体是通过精心设计的保护基操作合成的。我们发现，通过未受保护的糖类的位点选择性氧化形成的羰基可以转化为硫醇部分。该转化涉及用硫醇对氯偶氮中间体进行S N 1-取代，该中间体是通过相应的三苯甲基腙的氧化而形成的。所制备的脱氧硫代糖与最近开发的糖基氟化物的无保护基糖基化相结合，提供了硫代糖苷的无保护基合成。