(-)-(3aR,5R,6aR)-methyl 3a,5,6,6a-tetrahydro-2,2-dimethylfuro[2,3-d][1,3]dioxole-5-carboxylate | 35781-73-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(3aR,5R,6aR)-methyl 3a,5,6,6a-tetrahydro-2,2-dimethylfuro[2,3-d][1,3]dioxole-5-carboxylate
• 英文别名: 3-deoxy-1,2-O-(1-methylethylidene)-β-L-threo-pentofuranuronic acid, methyl ester；Methyl 3-deoxy-1,2-O-(1-methylethylidene)-beta-L-threo-pentofuranuronate；methyl (3aR,5R,6aR)-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole-5-carboxylate
• CAS: 35781-73-8
• 化学式: C₉H₁₄O₅
• 分子量: 202.207
• InChiKey: ZWEPQRRHDMLYIE-ATRFCDNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  (-)-(3aR,5R,6aR)-methyl 3a,5,6,6a-tetrahydro-2,2-dimethylfuro[2,3-d][1,3]dioxole-5-carboxylate 在 盐酸 、 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 73.0h， 生成 methyl (2R,4R,5R)-2-(hydroxymethyl)-5-methoxy-4-[(4-methoxyphenyl)methoxy]oxolane-2-carboxylate
  参考文献：
  名称：

  Synthesis of an enantiomerically pure 2,2,4-trisubstituted cyclobutanone building block by zirconocene-promoted deoxygenative ring contraction of structurally modified 4-vinylfuranosides

  摘要：

  A route to an enantiopure trisubstituted cyclobutanone has been devised. The pursuit of this building block begins With D-glucose and features a zirconocene-promoted ring contraction. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.07.012
• 作为产物：
  描述：

  1,2:5,6-di-O-isopropylidene-3-O-tosyl-α-D-glucofuranoside 在 sodium chlorite 、 sodium periodate 、 sodium dihydrogenphosphate 、 硫酸 、 双氧水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 20.0 ℃ 、275.8 kPa 条件下， 反应 22.0h， 生成 (-)-(3aR,5R,6aR)-methyl 3a,5,6,6a-tetrahydro-2,2-dimethylfuro[2,3-d][1,3]dioxole-5-carboxylate
  参考文献：
  名称：

  Synthesis of an enantiomerically pure 2,2,4-trisubstituted cyclobutanone building block by zirconocene-promoted deoxygenative ring contraction of structurally modified 4-vinylfuranosides

  摘要：

  A route to an enantiopure trisubstituted cyclobutanone has been devised. The pursuit of this building block begins With D-glucose and features a zirconocene-promoted ring contraction. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.07.012

文献信息

• The Carbohydrate−Sesquiterpene Interface. Directed Synthetic Routes to Both (+)- and (−)-Fomannosin from <scp>d</scp>-Glucose
  作者：Leo A. Paquette、Xiaowen Peng、Jiong Yang、Ho-Jung Kang

  DOI：10.1021/jo8004233

  日期：2008.6.1

  An enantiodivergent strategy for the total chemical synthesis of both naturally occurring (+)-fomannosin (1) and its (−)-antipode (ent-1) from α-d-glucose has been developed and successfully implemented. The key steps in the overall pathway include the following: (i) application of the zirconocene-mediated ring contraction of vinyl furanosides for the construction of highly substituted cyclobutanols;

  已开发并成功实施了一种自然化学（+）-fomannosin（1）及其从α- d-葡萄糖合成其（-）-antipode（ent - 1）的化学合成对映体策略。总体途径中的关键步骤包括：（i）锆茂茂介导的乙烯基呋喃糖苷的环收缩在构建高度取代的环丁醇中的应用；（ii）利用闭环复分解反应形成五元侧链。（iii）求助于单硫代丙二酸酯，以将其化学选择性还原成敏感的内酯中间体45；（iv）用OsO 4进行羟基定向的二羟基化反应，生成48; （v）通过环亚硫酸盐和三氟甲磺酸环丁酯顺序消除。对映体系列之间的桥由六步连接组成，涉及22的结构修饰以产生ent - 30b。光学活性在整个过程中被完全保留。
• Domino Aza-Claisen/Mannich Cyclization Reaction from a Chiral α-Alkoxy Enamine or Sequential Alkylation of an α-Alkoxy Ester Enolate or Nitrile Anion, Followed by an Intramolecular Wittig Reaction: Two (3+2) Annulation Routes to Homochiral 4-Alkyl-4-hydroxy-2-cyclopentenone Synthesis
  作者：Cyrille Kuhn、Leandros Skaltsounis、Claude Monneret、Jean-Claude Florent

  DOI：10.1002/ejoc.200300045

  日期：2003.7

  process is based on the sequential alkylation of esters 21, 39, or nitrile 20 with acetonyl equivalents 3 or 25, followed by an intramolecular Wittig reaction. As an application, the synthesis of the naturally occurring alkylidene-cyclopentenone prostaglandin clavulone II from the spiro[cyclopentene-furan]one 5 and the formal total synthesis of (+/-)-untenone 19 has been carried out. (© Wiley-VCH Verlag

  报道了对 4-烷基-4-羟基亚烷基-环戊烯酮前列腺素的对映选择性合成的研究。两个 (3+2) 环化过程允许合成同手性 4-烷基-4-羟基-2-环戊烯酮 4-5、10-11 和 17。第一个过程涉及多米诺氮杂-克莱森/曼尼希环化反应，得到来自α-烷氧基-烯胺的烷基化，衍生自手性α-烷氧基醛1、9或16，以3-碘-2-(甲氧基甲氧基)丙-1-烯(3)作为丙酮基等价物。第二个过程基于酯 21、39 或腈 20 与丙酮基等价物 3 或 25 的顺序烷基化，然后是分子内 Wittig 反应。作为应用程序，已经进行了由螺[环戊烯-呋喃]酮 5 合成天然存在的亚烷基-环戊烯酮前列腺素克拉维酮 II 和 (+/-)-untenone 19 的正式全合成。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Convergent synthesis of polyether ionophore antibiotics: an approach to the synthesis of the monensin tetrahydropyran-bis(tetrahydrofuran) via the ester enolate Claisen rearrangement and reductive decarboxylation
  作者：Robert E. Ireland、Daniel W. Norbeck、Gretchen S. Mandel、Neil S. Mandel

  DOI：10.1021/ja00297a039

  日期：1985.5
• A carbohydrate approach to 4-hydroxy-2-cyclopentenone moiety of antitumor prostanoid Punaglandin IV via alkylation of ester uronate
  作者：Cyrille Kuhn、Jean-Claude Florent

  DOI：10.1016/s0040-4039(98)00694-7

  日期：1998.6

  An efficient and stereoselective synthesis of a chiral precursor of 2-chloro-4-hydroxy-4-alkyl-2-cyclopentenone has been realized by alkylation of a sugar methyl uronate derived from 1,2-O-isopropylidene alpha-D-glucose with an acetonyl equivalent, and subsequent intramolecular Wittig reaction. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Synthesis of an enantiomerically pure 2,2,4-trisubstituted cyclobutanone building block by zirconocene-promoted deoxygenative ring contraction of structurally modified 4-vinylfuranosides
  作者：Leo A Paquette、Ho-Jung Kang

  DOI：10.1016/j.tet.2003.07.012

  日期：2004.2

  A route to an enantiopure trisubstituted cyclobutanone has been devised. The pursuit of this building block begins With D-glucose and features a zirconocene-promoted ring contraction. (C) 2003 Elsevier Ltd. All rights reserved.