3-O-allyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-xylo-hex-5-enofuranose | 226919-74-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-O-allyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-xylo-hex-5-enofuranose
• 英文别名: (3aR,5R,6S,6aR)-5-ethenyl-2,2-dimethyl-6-prop-2-enoxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole
• CAS: 226919-74-0
• 化学式: C₁₂H₁₈O₄
• 分子量: 226.273
• InChiKey: UFHYYBPEPYZFDJ-LMLFDSFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-O-allyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-xylo-hex-5-enofuranose 在 Grubbs catalyst first generation 、 sodium periodate 、 溶剂黄146 作用下， 以 水 、 丙酮 、 甲苯 为溶剂， 反应 7.0h， 生成 (2R,3R)-2-(hydroxymethyl)-3,6-dihydro-2H-pyran-3-ol
  参考文献：
  名称：

  从碳水化合物衍生物合成新型吡喃β-氨基酸和5,6-二氢-2H-吡喃β-氨氧基

  摘要：

  摘要 报道了从碳水化合物衍生物合成两种含有吡喃环的新氨基酸。顺-3-氨基-吡喃-2-羧酸（cis-APyC）由（R）-甘油醛衍生物制备，使用亲核取代反应形成吡喃环。类似地，反式-3-氨氧基-5,6-二氢-2H-吡喃-2-羧酸（反式-AmPyC）由双丙酮葡萄糖（DAG）制备，使用闭环复分解（RCM）反应形成环。图形概要

  DOI：

  10.1080/00397911.2015.1043018
• 作为产物：
  描述：

  3-O-allyl-1,2-O-isopropylidene-α-D-glucofuranose 在 咪唑 、 碘 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以12.3%的产率得到3-O-allyl-5,6-dideoxy-1,2-O-isopropylidene-α-D-xylo-hex-5-enofuranose
  参考文献：
  名称：

  从碳水化合物衍生物合成新型吡喃β-氨基酸和5,6-二氢-2H-吡喃β-氨氧基

  摘要：

  摘要 报道了从碳水化合物衍生物合成两种含有吡喃环的新氨基酸。顺-3-氨基-吡喃-2-羧酸（cis-APyC）由（R）-甘油醛衍生物制备，使用亲核取代反应形成吡喃环。类似地，反式-3-氨氧基-5,6-二氢-2H-吡喃-2-羧酸（反式-AmPyC）由双丙酮葡萄糖（DAG）制备，使用闭环复分解（RCM）反应形成环。图形概要

  DOI：

  10.1080/00397911.2015.1043018

文献信息

• Chiron Approach to Formal Synthesis of 8,9-dideoxyneodysiherbaine (MSVIII-19)
  作者：Alma Sanchez-Eleuterio、Virginia M. Mastranzo、Leticia Quintero、Fernando Sartillo-Piscil

  DOI：10.2174/1570178614666170307091943

  日期：2017.6.8

  Background: The synthesis of biologically active model compounds represents a valuable tool for medicinal chemistry. In this regard, the synthesis of MSVII-19, a structurally simplified model compound of Dysiherbaine, developed by the group of Sasaki, was synthesized with the intention of preparing a powerful agonist or antagonist of glutamate receptor. Therefore, the synthesis of an advanced intermediate in the Sasaki’s synthesis of MSVIII-19 is reported. Methods: Taking advantage of the furanose ring of the diacetone-D-glucose (DAG), the cis-fused hexahydrofuro[3,2-b]pyran ring system of the title compound was constructed by featuring two protocols: SHOWO (sequential hydrolysis-oxidation-Wittig olefination) and RCM (ring closing metathesis). Then, by applying a combined allylation at the anomeric position and a Pd-catalyzed double bond isomerization reaction, the methyl ester group in 1b was installed. Results: The synthesis of an advanced intermediate of MSVIII-19 involves three key procedures: a) SHOWO (sequential hydrolysis-oxidation-Wittig olefination) protocol; b) RCM (ring closing metathesis) reaction; y c) the nucleophilic substitution at the anomeric position. Additionally, with the use of a cheaper starting material (DAG) than that used in the previous synthesis (tri-O-acetyl-D-glucal). The current synthesis is truly competitive with that reported by the Sasaki group. Conclusion: A concise formal total synthesis of the advanced intermediate of MSVIII-19 was achieved. (Current synthesis: 14 steps; previous synthesis 20 steps).

  背景：生物活性模型化合物的合成是药物化学中的一项重要工具。在这方面，由佐佐木团队开发的结构简化的Dysiherbaine模型化合物MSVIII-19的合成旨在制备强效的谷氨酸受体激动剂或拮抗剂。因此，报告了佐佐木合成MSVIII-19中一个高级中间体的合成。 方法：利用二乙酮-D-葡萄糖（DAG）的呋喃环，通过两个步骤构建了标题化合物的顺式融合六氢呋喃[3,2-b]吡喃环系统：SHOWO（顺序水解-氧化-Wittig烯化）和RCM（环闭合烯烃交换反应）。然后，通过在异头位置应用联合烯丙基化和Pd催化的双键异构化反应，以安装1b中的甲基酯基团。 结果：MSVIII-19高级中间体的合成涉及三个关键程序：a) SHOWO（顺序水解-氧化-Wittig烯化）协议；b) RCM（环闭合烯烃交换）反应；c) 在异头位置的亲核取代。此外，使用了比先前合成中使用的起始材料（tri-O-乙酰-D-葡萄糖醛）更便宜的起始物质（DAG）。目前的合成与佐佐木团队报告的合成相比，具有较强的竞争力。 结论：成功实现了MSVIII-19高级中间体的简洁正式总合成。（当前合成：14步；先前合成：20步）。
• Haque, Azizul; Panda, Jagannath; Ghosh, Subrata, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1999, vol. 38, # 1, p. 8 - 9
  作者：Haque, Azizul、Panda, Jagannath、Ghosh, Subrata

  DOI：——

  日期：——
• Deoxygenation/dimerization of sugar derivatives with BF3·Et2O–Et3SiH: synthesis of a β-isonucleoside
  作者：Subhrangshu Mukherjee、Biswajit G. Roy、Soumendra N. Das、Sukhendu B. Mandal

  DOI：10.1016/j.tetlet.2012.06.121

  日期：2012.9

  Lewis acid-Et3SiH induced deoxygenation of anomeric carbon of sugars generates tetrahydrofuran derivatives, accompanied by hitherto unknown dimeric products. If the reagent addition steps are reversed, tetrahydrofuran derivatives are obtained as the sole products, while only the dimeric products are isolated if Et3SiH is excluded. One of the deoxygenated products has been transformed into a beta-isonucleoside. (C) 2012 Elsevier Ltd. All rights reserved.
• RCM/PCC oxidation strategy for synthesis of functionalized cyclic α,β-unsaturated lactones: synthesis of (+)-triacetoxygoniotriol and its diastereomers
  作者：G.S.C. Srikanth、Urlam Murali Krishna、Girish K. Trivedi、John F. Cannon

  DOI：10.1016/j.tet.2006.09.016

  日期：2006.11

  A novel methodology leading to the synthesis of (+)-triacetoxygoniotriol 2 from D-glucose is described. Construction of the core six-membered alpha, beta-unsaturated lactone moiety involved ring closing metathesis (RCM) followed by a PCC oxidation. Later exploiting the pseudo-symmetry of D-glucose three other diastereomers of triacetoxygoniotriol were synthesized using the developed methodology. (c) 2006 Elsevier Ltd. All rights reserved.
• A convenient route to cis- and trans-fused bicyclic ethers by ruthenium mediated ring-closing metathesis of diene and enyne carbohydrate derivatives
  作者：Michiel A. Leeuwenburgh、Camiel Kulker、Howard I. Duynstee、Herman S. Overkleeft、Gijsbert A. van der Marel、Jacques H. van Boom

  DOI：10.1016/s0040-4020(99)00296-3

  日期：1999.7

  A general approach towards the construction of highly functionalised pyranopyran and pyranofuran systems via Grubbs [Ru] catalysed ring-closing metatheses of neighbouring vinyl-O-allyl and vinyl-O-propargyl functions on monosaccharide scaffolds is described. (C) 1999 Elsevier Science Ltd. All rights reserved.