methyl 4,6-O-benzylidene-2-deoxy-2-C-propenyl-α-D-erythro-hexopyranosid-3-ulose | 138750-12-6

• 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-2-deoxy-2-C-propenyl-α-D-erythro-hexopyranosid-3-ulose
• 英文别名: Methyl 2-C-allyl-4,6-O-benzylidene-α-D-ribo-hexopyranosid-3-ulose；(2R,4aR,6S,7S,8aR)-6-methoxy-2-phenyl-7-prop-2-enyl-4a,6,7,8a-tetrahydro-4H-pyrano[3,2-d][1,3]dioxin-8-one
• CAS: 138750-12-6
• 化学式: C₁₇H₂₀O₅
• 分子量: 304.343
• InChiKey: RQYXZQKHXVBCBU-HSMRXVHUSA-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-2-deoxy-2-C-propenyl-α-D-erythro-hexopyranosid-3-ulose 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 吡啶 、 sodium tetrahydroborate 、 溶剂黄146 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 58.0h， 生成 (2R,4aR,6S,6aR,11aS,11bS)-6-Methoxy-2-phenyl-4a,6,6a,7,10,11,11a,11b-octahydro-4H-1,3,5-trioxa-11-aza-cyclohepta[a]naphthalene
  参考文献：
  名称：

  A ring-closing metathesis route to 7-membered aza-heteroannulated sugars

  摘要：

  Azepane rings have been constructed diastereoselectively upon a carbohydrate derivative utilising reductive amination and RCM. The stereochemistry of the ring junctions was confirmed by X-ray crystallography and NMR. Diastereo selective dihydroxylation has also been employed to afford a tetrahydroxylated azepane carbohydrate derivative with potential biological activity. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.02.007
• 作为产物：
  描述：

  methyl 4,6-O-benzylidene-2-deoxy-2-(2-propenyl)-α-D-allohexopyranoside 在 二甲基亚砜 、 三乙胺 、 三氟乙酸酐 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 49.5h， 生成 methyl 4,6-O-benzylidene-2-deoxy-2-C-propenyl-α-D-erythro-hexopyranosid-3-ulose
  参考文献：
  名称：

  The Stereoselective Preparation of an Enantiomerically Pure Cyclopentane Using Intramolecular Aldol Cyclopentaannulation of a Glucose Derivative

  摘要：

  Methods for the annulation of carbohydrates have found extensive applications in organic synthesis. We report here a new protocol for the stereoselective conversion of glucose into an enantiomerically pure cyclopentane aldehyde 22. The readily available epoxide 15 was reacted with allyl Grignard to produce alcohol 16 in 86% yield. Swern oxidation followed by epimerization using triethylamine in N,N-dimethylformamide furnished the ketone 17 also in 86% yield. Regioselective deprotonation with lithium hexamethyldisilazane in THF was followed by methylation with methyl iodide and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidone as cosolvent to give 80% yield of ketone 18. Oxidation of ketone 18 by the Wacker procedure gave the 1,4-diketone 19 in 56% yield. Intramolecular aldol condensation occurred readily on treatment of diketone 19 with potassium tert-butoxide in toluene to furnish a 90% yield of enone 20. Treatment with N-bromosuccinimide produced the bromoester 21 in 72% yield, which was reduced to a mixture of aldehydes 22 (61%) and 23 (14%) with zinc shot in 2-propanol.

  DOI：

  10.1021/jo981225j

文献信息

• 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。
• 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。
• Stereoselective synthesis of seven-membered lactams and lactones on a carbohydrate scaffold using ring-closing metathesis
  作者：Dominic L. Laventine、Paul M. Cullis、Marcos D. García、Paul R. Jenkins

  DOI：10.1016/j.tetlet.2009.03.125

  日期：2009.7

  electron-deficient α,β-unsaturated amides and esters leading to the synthesis of enantiopure azepinone and oxepinone derivatives on a carbohydrate glycoside scaffold. The relative stereochemistries of the compounds obtained were corroborated by X-ray crystallography, 1H NMR or deduced based on previously reported results. These compounds are designed as precursors of new polyhydroxylated heteroannulated

  我们在这里介绍了Grubbs第二代催化剂在缺电子的α，β-不饱和酰胺和酯的闭环易位反应中的应用，从而导致在碳水化合物糖苷骨架上合成对映体纯的ze庚酮和oxepinone衍生物。通过X射线晶体学，1 H NMR证实了所获得的化合物的相对立体化学，或者根据先前报道的结果推导了该相对立体化学。这些化合物被设计为具有潜在生物活性的新型多羟基杂化糖的前体。