methyl 4,6-O-benzylidene-3-deoxy-3-C-propenyl-α-D-arabino-hexopyranoside-2-ulose | 135700-48-0

• 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 4,6-O-benzylidene-3-deoxy-3-C-propenyl-α-D-arabino-hexopyranoside-2-ulose
• 英文别名: methyl 3-C-allyl-4,6-O-(phenylmethylene)-α-D-arabino-hexopyranosid-2-ulose；Methyl 3-C-allyl-4,6-O-benzylidene-α-D-arabino-hexopyranosid-2-ulose；(2R,4aR,6S,8S,8aS)-6-methoxy-2-phenyl-8-prop-2-enyl-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3]dioxin-7-one
• CAS: 135700-48-0
• 化学式: C₁₇H₂₀O₅
• 分子量: 304.343
• InChiKey: GUCXWAWTRVAMQZ-GJVDQKBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-benzylidene-3-deoxy-3-C-propenyl-α-D-arabino-hexopyranoside-2-ulose 在 polymer-bound PPh₃ 、 臭氧 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 2.0h， 生成 methyl α-D-4,6-O-((R)-benzylidene)-3-deoxy-3-(2-oxoethyl)-glucopyranosid-2-ulose
  参考文献：
  名称：

  Ring-closing double reductive amination route to aza-heteroannulated sugars

  摘要：

  1.4-Dicarbonyl derivatives of glycosides are produced by ozonolysis or Wacker oxidation. A stable ozonide is isolated and a carbonyl group reduced whilst maintaining the ozonide functionality. The 1,4-dicarbonyl compounds are converted to various N-substituted pyrrolidines by diastereoselective double reductive amination The resulting aza-heteroannulated sugars no significant inhibition of any glycosidase, with the exception of compound 12g. which is a weak inhibitor Of beta-galactosidase. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.11.032
• 作为产物：
  描述：

  methyl 2,3-anhydro-4,6-O-benzilidene-α-D-mannopyranoside 在 sodium hydride 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 二甲基亚砜 、 xylene 为溶剂， 反应 1.67h， 生成 methyl 4,6-O-benzylidene-3-deoxy-3-C-propenyl-α-D-arabino-hexopyranoside-2-ulose
  参考文献：
  名称：

  己烯吡喃糖苷烯丙基醚的克莱森重排：α-支链二羰基糖的新方法

  摘要：

  摘要将2，3-脱水吡喃糖苷与苯基硒化钠裂解制备的β-羟基苯基硒化物被定量转化为相应的烯丙基醚。烯丙基醚的氧化，然后进行热消除和重排，以高收率得到C-烯丙基己糖。醚10a和10c的重排特别是立体选择性的，得到轴向取向的C-烯丙基己糖衍生物，其易于以定量产率差向为其赤道异构体。在巴豆醚14c的克莱森重排中，糖的手性转移到新形成的不对称碳原子上。该程序提供了将脱水糖转化为C-烯丙基己糖衍生物的便利方法。

  DOI：

  10.1016/0008-6215(91)80006-9

文献信息

• Stereoselective Preparation of Enantiomerically Pure Annulated Carbohydrates Using Ring-Closing Metathesis
  作者：David J. Holt、William D. Barker、Paul R. Jenkins、Jagannath Panda、Subrata Ghosh

  DOI：10.1021/jo991392z

  日期：2000.1.1

  Ring-closing metathesis has been applied to a series of glucose derivatives to produce cyclopentene derivatives 5a and 5b, cyclohexene derivatives 8 and 9, cycloheptene 12, and cyclooctene 14. Spirocyclic dihydrofurans 19, 26a, and 26b, along with dihydropyran 22, were also produced. A range of fused oxepine derivatives 29a-c and one oxo-cyclononene 31 were also prepared. Cyclopentene 5b was subjected

  闭环复分解已应用于一系列葡萄糖衍生物以产生环戊烯衍生物5a和5b，环己烯衍生物8和9，环庚烯12和环辛烯14。还与二氢吡喃22一起形成了环二氢呋喃19、26a和26b。生产的。还制备了一系列稠合的氧杂环丁烷衍生物29a-c和一个氧代-环壬烯31。对环戊烯5b进行一系列的氢化，NBS溴化处理，然后用锌粉处理以提供扩环产物35。当先用NBS处理环六环化合物8，再用锌粉处理后，这样的扩环就不会发生，从而生成醛39通过用于使环戊烯衍生物5b断裂的相同反应顺序，将螺二氢呋喃衍生物19转化为醛42。
• Ring-Closing Metathesis in Carbohydrate Annulation
  作者：David J. Holt、William D. Barker、Paul R. Jenkins、David L. Davies、Shaun Garratt、John Fawcett、David R. Russell、Subtrata Ghosh

  DOI：10.1002/(sici)1521-3773(19981217)37:23<3298::aid-anie3298>3.0.co;2-o

  日期：1998.12.17

  Even eight-membered rings (such as in 2) can be formed by ring-closing metathesis of glucose derivatives such as 1. Enantiomerically pure tricyclic spiro compounds can also be prepared.

  通过葡萄糖衍生物例如1的开环易位，甚至可以形成八元环（例如在2中）。也可以制备对映体纯的三环螺化合物。
• Claisen rearrangement of hexenopyranoside allyl ethers: A new approach to α-branched-chain dicarbonyl sugars
  作者：Kimiaki Furuichi、Hiromasa Hashimoto、Toshio Miwa

  DOI：10.1016/0008-6215(91)80006-9

  日期：1991.11

  corresponding allyl ethers. Oxidation of the allyl ethers, followed by thermal elimination and rearrangement, gave C -allylhexosuloses in good yield. Rearrangement of ethers 10a and 10c was especially stereoselective, giving axially oriented C -allylhexosulose derivatives, which were readily epimerized to their equatorial isomers in quantitative yield. In the Claisen rearrangement of the crotyl ether 14c ,

  摘要将2，3-脱水吡喃糖苷与苯基硒化钠裂解制备的β-羟基苯基硒化物被定量转化为相应的烯丙基醚。烯丙基醚的氧化，然后进行热消除和重排，以高收率得到C-烯丙基己糖。醚10a和10c的重排特别是立体选择性的，得到轴向取向的C-烯丙基己糖衍生物，其易于以定量产率差向为其赤道异构体。在巴豆醚14c的克莱森重排中，糖的手性转移到新形成的不对称碳原子上。该程序提供了将脱水糖转化为C-烯丙基己糖衍生物的便利方法。
• The synthesis and X-ray crystal structure of a cyclopentaannulated sugar; the first example of an intramolecular aldol cyclopentaannulation in carbohydrate chemistry
  作者：Andrew J. Wood、Paul R. Jenkins、John Fawcett、David R. Russell

  DOI：10.1039/c39950001567

  日期：——

  A 1,4-dicarbonyl compound 5 has been constructed by a sequence involving opening of a protected glucose epoxide with allyl magnesium chloride, alkylation and Wacker oxidation; the 1,4-dicarbonyl compound readily undergoes cyclisalion under basic conditions to produce a Cyclopentaannulated sugar derivative 6, whose structure was confirmed by X-ray crystallography.

  在碱性条件下，1,4-二羰基化合物很容易发生环化反应，生成环戊二烯糖衍生物 6。
• Stereoselective synthesis by double reductive amination ring closure of novel aza-heteroannulated sugars
  作者：Dominic M. Laventine、Michelle Davies、Emma L. Evinson、Paul R. Jenkins、Paul M. Cullis、Marcos D. García

  DOI：10.1016/j.tet.2009.04.011

  日期：2009.6

  We present here the stereoselective synthesis of a series of 2/3-N-pyrrolidine derivatives of glycosides produced by diastereoselective double reductive amination ring closure of 1,4-dicarbonyl compounds. These precursors were produced by tandem ozonolysis–reduction or Wacker oxidation of known alkenes. The potential of these new compounds as glycosidase inhibitors is illustrated for compound 16, showing

  我们在这里介绍了由1，4-二羰基化合物的非对映选择性双还原胺化闭环产生的一系列2 / 3- N-吡咯烷糖苷衍生物的立体选择性合成。这些前体是通过串联臭氧分解-还原或瓦克氧化已知烯烃而制得的。这些新化合物作为糖苷酶抑制剂的潜力在化合物16中得到了说明，显示出对β- d-半乳糖苷酶的选择性抑制。