methyl (3aS,4R,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,7a-dihydro-4H-[1,3]dioxolo[4,5-c]pyran-6-carboxylate | 107961-76-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: methyl (3aS,4R,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,7a-dihydro-4H-[1,3]dioxolo[4,5-c]pyran-6-carboxylate
• 英文别名: methyl 2,6-anhydro-3-deoxy-4,5:7,8-di-O-isopropylidene-D-manno-oct-2-enosonate；methyl (3aR,4R,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-4,7a-dihydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-carboxylate
• CAS: 107961-76-2
• 化学式: C₁₅H₂₂O₇
• 分子量: 314.335
• InChiKey: URBHDQHATHBSIL-HJQYOEGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  72.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl (3aS,4R,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,7a-dihydro-4H-[1,3]dioxolo[4,5-c]pyran-6-carboxylate 在 W-2 Raney nickel 氢气 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以88%的产率得到methyl 2,6-anhydro-3-deoxy-4,5:7,8-di-O-isopropylidene-D-glycero-D-galacto-octonate
  参考文献：
  名称：

  Synthesis of an isosteric phosphonate analog of cytidine 5'-monophospho-3-deoxy-D-manno-2-octulosonic acid

  摘要：

  DOI：

  10.1021/jo00387a011
• 作为产物：
  描述：

  1,2-dideoxy-4,5:7,8-di-O-isopropylidene-D-erythro-D-manno-1-yno-octitol 在 4-二甲氨基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 palladium 10% on activated carbon 、 氢气 、 sodium hydride 、 碳酸氢钠 、 magnesium sulfate 、 silver nitrate 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 甲醇 、 水 、 乙酸乙酯 、 丙酮 、 乙腈 、 mineral oil 为溶剂， 反应 18.75h， 生成 methyl (3aS,4R,7aR)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-3a,7a-dihydro-4H-[1,3]dioxolo[4,5-c]pyran-6-carboxylate
  参考文献：
  名称：

  受保护的3-脱氧-d-甘露糖-辛-2-磺酸酯类葡萄糖供体的制备，用于合成含β-KDO的寡糖

  摘要：

  开发了一种实用的合成KDO葡萄糖供体的方法。制备的KDO供体在CH 2 Cl 2 -CH 3 CN溶剂混合物中显示出极好的糖基化的对映选择性，发现与C-4和C-5羟基处的异亚丙基保护有关。在含β-KDO的寡糖的制备中证明了KDO供体的合成用途。

  DOI：

  10.1021/ol500275j

文献信息

• A light- and heat-driven glycal diazidation approach to nitrogenous carbohydrate derivatives with antiviral activity
  作者：Huan He、Ruiyuan Cao、Ruidi Cao、Xiao-Yu Liu、Wei Li、Di Yu、Yuexiang Li、Miaomiao Liu、Yanmei Wu、Pingzhou Wu、Jin-Song Yang、Yunzheng Yan、Jingjing Yang、Zhi-Bing Zheng、Wu Zhong、Yong Qin

  DOI：10.1039/d0ob01172j

  日期：——

  The aminated mimetics of 2-keto-3-deoxy-sugar acids such as the anti-influenza clinical drugs oseltamivir (Tamiflu) and zanamivir (Relenza) are important bioactive molecules. Development of synthetic methodologies for accessing such compound collections is highly desirable. Herein, we describe a simple, catalyst-free glycal diazidation protocol enabled by visible light-driven conditions. This new method

  2-keto-3-deoxy-sugar 酸的胺化模拟物，如抗流感临床药物奥司他韦（达菲）和扎那米韦（Relenza）是重要的生物活性分子。开发用于访问此类化合物集合的合成方法是非常可取的。在这里，我们描述了一种由可见光驱动条件启用的简单、无催化剂的糖基二叠氮化协议。这种新方法既不需要酸助剂也不需要过渡金属催化剂，并且在环境温度下可在 1-2 小时内完成。值得注意的是，热条件也可以促进所需的转化，尽管与光诱导条件相比效率较低。通过利用这种温和且可扩展的方法，已将不同的糖酸衍生的糖模板转化为一系列 2,3-二叠氮基碳水化合物类似物，
• An In-Depth Study on Ring-Closing Metathesis of Carbohydrate-Derived α-Alkoxyacrylates:  Efficient Syntheses of DAH, KDO, and 2-Deoxy-β-KDO
  作者：Koen F. W. Hekking、Marcel A. H. Moelands、Floris L. van Delft、Floris P. J. T. Rutjes

  DOI：10.1021/jo060913x

  日期：2006.8.1

  Novel, efficient synthetic pathways to DAH, KDO, and 2-deoxy-β-KDO are described. Ring-closing metathesis (RCM) of highly functionalized α-alkoxyacrylate fragments resulted in a series of synthetically versatile oxygen heterocyclic intermediates. Further functionalization of the resulting enol ether double bond and subsequent deprotection provided the natural products in high overall yields, starting

  描述了通往DAH，KDO和2-deoxy-β-KDO的新颖，有效的合成途径。高度官能化的α-烷氧基丙烯酸酯片段的闭环复分解（RCM）导致了一系列合成上通用的氧杂环中间体。从可商购的被保护的糖开始，所得烯醇醚双键的进一步官能化和随后的脱保护以高的总收率提供了天然产物。
• Synthesis of Allyl 3-Deoxy-D-<i>manno</i>-2-octulopyranosidic Acid 4- and 5-Phosphates
  作者：Koichi Fukase、Takashi Kamikawa、Yukari Iwai、Tetsuo Shiba、Ernst Theodor Rietschel、Shoichi Kusumoto

  DOI：10.1246/bcsj.64.3267

  日期：1991.11

  Allyl glycosides (ketosides) of pyranosidic 3-deoxy-d-manno-2-octulosonic acid (Kdo), phosphorylated at either positions 4 or 5 were synthesized with the aim to study the biological properties of phosphorylated Kdo. The α and β-allyl glycosides prepared from a pyranosidic fluoride of diisopropylidene Kdo were protected at the 7- and 8-positions, and then O-phosphorylated at the 4- or 5-position by the phosphoramidite procedure. Separation of the positional isomers followed by deprotection afforded four compounds in pure states.

  对3-脱氧-D-甘露-2-辛酮糖酸（Kdo）的烯丙基糖苷（酮糖苷）在4或5号位进行磷酸化，以研究磷酸化Kdo的生物特性。从二异丙基Kdo的吡喃糖苷氟化物制备的α和β-烯丙基糖苷在7和8号位进行保护，然后通过亚磷酰胺方法在4或5号位进行O-磷酸化。分离位置异构体，然后进行脱保护，得到四种纯态化合物。
• Evaluation of thioglycosides of Kdo as glycosyl donors
  作者：Karin Mannerstedt、Kerstin Ekelöf、Stefan Oscarson

  DOI：10.1016/j.carres.2006.08.021

  日期：2007.2

  The use of Kdo thioglycosides as glycosyl donors using DMTST, IBr/AgOTf and NIS/AgOTf as promoters has been evaluated. Activation at low temperature allowed to escape the formation of 2,3-glycal byproducts to give glycosides in high yield and with good beta-anomeric selectivity. The use of diethyl ether as solvent and (especially) isopropylidene acetals as protecting groups improved the alpha-anomeric selectivity. NIS/AgOTf as promoter surprisingly yielded the 3-iodo-product via the glycal intermediate. (c) 2006 Elsevier Ltd. All rights reserved.
• Ring-closing metathesis of α-ester-substituted enol ethers: application to the shortest synthesis of KDO
  作者：Koen F.W Hekking、Floris L van Delft、Floris P.J.T Rutjes

  DOI：10.1016/s0040-4020(03)00819-6

  日期：2003.8

  Ring-closing metathesis reactions of alpha-ester-substituted enol ethers are described. In the case of unsubstituted terminal olefins, isomerization prior to cyclization was observed as an undesired side reaction, which could not be completely inhibited. Furthermore, this methodology was applied to a formal synthesis of KDO, which now represents the shortest synthetic pathway to KDO and its deoxy analogue. Interestingly, in this route olefin isomerization was not observed, presumably due to the increased steric environment of the double bond. Finally, an efficient two-step conversion to transform an alcohol into an alpha-alkoxy acrylate is also described. (C) 2003 Elsevier Ltd. All rights reserved.