methyl 2-deoxy-2-iodo-4,6-O-(phenylmethylene)-α-D-mannopyranoside | 517893-16-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2-deoxy-2-iodo-4,6-O-(phenylmethylene)-α-D-mannopyranoside
• 英文别名: methyl 2-deoxy-2-iodo-4,6-O-benzylidene-α-D-mannopyranoside；methyl 4,6-O-benzylidene-2-deoxy-2-iodo-α-D-mannopyranoside；(2R,4aR,6S,7S,8S,8aS)-7-iodo-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-ol
• CAS: 517893-16-2
• 化学式: C₁₄H₁₇IO₅
• 分子量: 392.19
• InChiKey: NAKXGYCEKCJLJM-LEZGYBIHSA-N

物化性质

• 熔点：
  94-96 °C(Solv: ligroine (8032-32-4))
• 沸点：
  501.3±50.0 °C(Predicted)
• 密度：
  1.70±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2-deoxy-2-iodo-4,6-O-(phenylmethylene)-α-D-mannopyranoside 在 dihydrogen hexachloroplatinate(IV) hexahydrate 、 溶剂黄146 、 锌 作用下， 以 二氯甲烷 为溶剂， 反应 1.08h， 以59%的产率得到4,6-O-benzylidene-D-glucal
  参考文献：
  名称：

  3,4-反式稠环保护基团促进α-选择性催化合成2-脱氧糖苷

  摘要：

  已经开发出一种实用的方法，使用反式稠合环状 3,4-O-二硅氧烷保护基团和 TsOH⋅H 2 O ，将葡糖和鼠李糖转化为具有高α-选择性和产率（77-97%）的二糖或糖缀合物（ 1 mol%) 作为催化剂。异头选择性的控制来自中间氧杂碳鎓阳离子的构象锁定。Glucals 优于鼠李糖醇，因为 C6 侧链构象增强了选择性。

  DOI：

  10.1002/anie.201403543
• 作为产物：
  描述：

  4,6-O-benzylidene-1-O-methyl-2-O-trifluoromethylsulfonate-α-D-glucopyranoside 在 四丁基碘化铵 作用下， 以 甲苯 为溶剂， 反应 4.0h， 以90%的产率得到methyl 2-deoxy-2-iodo-4,6-O-(phenylmethylene)-α-D-mannopyranoside
  参考文献：
  名称：

  3,4-反式稠环保护基团促进α-选择性催化合成2-脱氧糖苷

  摘要：

  已经开发出一种实用的方法，使用反式稠合环状 3,4-O-二硅氧烷保护基团和 TsOH⋅H 2 O ，将葡糖和鼠李糖转化为具有高α-选择性和产率（77-97%）的二糖或糖缀合物（ 1 mol%) 作为催化剂。异头选择性的控制来自中间氧杂碳鎓阳离子的构象锁定。Glucals 优于鼠李糖醇，因为 C6 侧链构象增强了选择性。

  DOI：

  10.1002/anie.201403543

文献信息

• A robust synthesis of N-glycolyl muramyl dipeptide via azidonitration/reduction
  作者：Shuo Xing、James L. Gleason

  DOI：10.1039/c4ob02147a

  日期：——

  Glycal etherification followed by azidonitration/reduction solves a difficult S_N2 step in the synthesis of N-glycolyl muramyl dipeptide.

  糖醛醚化后接着进行叠氮硝化/还原，解决了在合成N-糖氧基muramyl二肽中的一个困难SN2步骤。

• Stereoselective Synthesis of α-Linked 2-Deoxy Glycosides Enabled by Visible-Light-Mediated Reductive Deiodination
  作者：Hao Wang、Jinyi Tao、Xinpei Cai、Wei Chen、Yueqi Zhao、Yang Xu、Wang Yao、Jing Zeng、Qian Wan

  DOI：10.1002/chem.201405516

  日期：2014.12.22

  2‐Deoxy sugars and their derivatives occur abundantly in many pharmaceutically important natural products. However, the construction of specific 2‐deoxy‐glycosidic bonds remains as a challenge. Herein, we report an efficient way to prepare 2‐deoxy‐α‐glycosides by glycosylation of 2‐iodo‐glycosyl acetate and subsequent visible‐light‐mediated tin‐free reductive deiodination. We have successfully applied

  2-脱氧糖及其衍生物大量存在于许多重要的天然药物中。然而，具体的2-脱氧糖苷键的构建仍然是一个挑战。在此，我们报告了一种通过2-碘-糖基乙酸乙酸酯的糖基化和随后的可见光介导的无锡还原脱碘来制备2-脱氧-α-糖苷的有效方法。我们已成功地将糖基化后去碘化策略应用于30多种单糖，二糖，三糖，四糖和十五糖的合成，并具有出色的立体选择性和效率。该方法也已用于合成包含四个α-键的2-脱氧四糖。
• Glycosylation Enabled by Successive Rhodium(II) and Brønsted Acid Catalysis
  作者：Lingkui Meng、Peng Wu、Jing Fang、Ying Xiao、Xiong Xiao、Guangsheng Tu、Xiang Ma、Shuang Teng、Jing Zeng、Qian Wan

  DOI：10.1021/jacs.9b04619

  日期：2019.7.31

  reaction comprises two chronological meticulously-designed catalytic cycles: 1) rhodium-catalyzed formation of sulfonium ylide; 2) Brønsted acid-catalyzed formation of sulfonium ion. This protocol highlight-ed an effective and robust tactic to prepare glycosyl sulfonium ion from glycosyl sulfonium ylide precursor amenable for glycosylation.

  在此，我们报道了一种高效的糖基化反应，包括两个按时间顺序精心设计的催化循环：1）铑催化形成锍叶立德；2) Brønsted 酸催化形成锍离子。该协议强调了一种有效且稳健的策略，可从适合糖基化的糖基锍叶立德前体制备糖基锍离子。
• The First Radical Method for the Introduction of an Ethynyl Group Using a Silicon Tether and Its Application to the Synthesis of 2‘-Deoxy-2‘-<i>C</i>-ethynylnucleosides¹
  作者：Makoto Sukeda、Satoshi Ichikawa、Akira Matsuda、Satoshi Shuto

  DOI：10.1021/jo0206667

  日期：2003.5.1

  A novel radical method for the stereoselective introduction of an ethynyl group has been developed. When a solution of ethynyldimethylsilyl (EDMS) or [2-(trimethylsilyl)ethynyl]dimethylsilyl (TEDMS) ethers of trans-2-iodoindanol was treated with Et3B followed by tetrabutylammonium fluoride in toluene, atom transfer 5-exo-cyclization and subsequent elimination occurred to give cis-2-ethynylindanol in high yield. The method was shown to be useful in the introduction of an ethynyl group in various five- and six-membered-ring iodohydrins. Furthermore, 2'-deoxy-2'-C-ethynyl-uridine (6) and -cytidine (7), which were designed as novel antimetabolites, were readily synthesized by using this method as the key step. This would be the first example in which a radical reaction was used for introducing an ethynyl group.
• A facile synthesis of 4,6-O-benzylidene glucal
  作者：David J. Chambers、Graham R. Evans、Antony J. Fairbanks

  DOI：10.1016/s0957-4166(03)00288-x

  日期：2003.7

  4,6-O-Benzylidene protected D-glucal, a useful synthetic intermediate, may be accessed from the extremely cheap and readily available starting material alpha-methyl glucopyranoside, via a simple four-step reaction sequence involving selective triflation and iodide displacement at C-2. (C) 2003 Elsevier Science Ltd. All rights reserved.