(E,4'S,5'S)-ethyl 3-(2',2',5'-trimethyl-1',3'-dioxolan-4'-yl)acrylate | 73679-53-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E,4'S,5'S)-ethyl 3-(2',2',5'-trimethyl-1',3'-dioxolan-4'-yl)acrylate
• 英文别名: ethyl (E)-3-((4S,5S)-2,2,5-trimethyl-1,3-dioxolan-4-yl)acrylate；(E)-ethyl 3-((4S,5S)-2,2,5-trimethyl-1,3-dioxolan-4-yl)acrylate；(4S,5S,2E)-methyl 4,5-isopropylidenedioxyhept-2-enoate；ethyl (E)-3-[(4S,5S)-2,2,5-trimethyl-1,3-dioxolan-4-yl]prop-2-enoate
• CAS: 73679-53-5
• 化学式: C₁₁H₁₈O₄
• 分子量: 214.262
• InChiKey: VGTQJPOZNSKQMW-YKAJXJTPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E,4'S,5'S)-ethyl 3-(2',2',5'-trimethyl-1',3'-dioxolan-4'-yl)acrylate 在 甲基磺酰胺 、 potassium carbonate 四氧化锇 、 camphor-10-sulfonic acid 、 二异丁基氢化铝 、 氢化奎尼定 1,4-(2,3-二氮杂萘)二醚 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 36.5h， 生成 ((4R,5S)-2,2-dimethyl-5-((4R,5S)-2,2,5-trimethyl-1,3-dioxolan-4-yl)-1,3-dioxolan-4-yl)methanol
  参考文献：
  名称：

  Enantioselective Synthesis of 10-epi-Anamarine via an Iterative Dihydroxylation Sequence

  摘要：

  The enantioselective syntheses of 10-epi-anamarine and 5,10-epi,epi-anamarine have been achieved in 13 to 14 steps. The route relies upon an enantio- and regioselective Sharpless dihydroxylation of either dienoates or trienoates to establish the C-8 to C-11 stereochemistry. A diastereoselective Leighton allylation established the desired C-5 stereochemistry. The route also relies upon a ring-closing metathesis to establish the alpha,beta-unsaturated lactones.

  DOI：

  10.1021/ol047322i
• 作为产物：
  描述：

  山梨酸乙酯 在 四氧化锇 、 Hydroquinone 1,4-phthalazinediyl diether 甲基磺酰胺 、 camphor-10-sulfonic acid 、 potassium carbonate 、 potassium hexacyanoferrate(III) 作用下， 以 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 3.0h， 生成 (E,4'S,5'S)-ethyl 3-(2',2',5'-trimethyl-1',3'-dioxolan-4'-yl)acrylate
  参考文献：
  名称：

  De Novo Enantioselective Syntheses of Galacto-Sugars and Deoxy Sugars via the Iterative Dihydroxylation of Dienoate

  摘要：

  [GRAPHICS]An efficient route to various sugar lactones has been developed. Key to the overall transformation is the sequential osmium-catalyzed dihydroxylation of 2,4-dienoates. The simplest (one-step/racemic) example of this reaction occurs when the dihydroxylation is performed with aqueous NMO in MeOH. When the first dihydroxylation is performed using the AD-mix procedure, an enantioselective variant results. When a matched AD-mix procedure is used for the second dihydroxylation, an exceedingly diastereo- and enantioselective synthesis of galacto-1,4-lactone results.

  DOI：

  10.1021/ol050044i

文献信息

• Towards novel amide-modified oligonucleotides: asymmetric synthesis of 5′-(S)-methyl-3′-carboxymethylene-3′-deoxythymidine
  作者：Sebastian Wendeborn、Hannes Nussbaumer、Frédéric Robert、Mario Jörg、Johannes Paul Pachlatko

  DOI：10.1016/s0040-4039(02)01053-5

  日期：2002.7

  xymethylene-3′-deoxythymidine is reported. Key steps involve diastereoselective lactonization, enantioselective enzymatic ester hydrolysis and diastereoselective glycosidation of a key intermediate with thymine with 100% β-selectivity via Lewis acid mediated cleavage of a [3.2.1] oxabicyclic lactone.

  报道了新颖的5'-（S）-甲基-3'-羧亚甲基-3'-脱氧胸苷的合成。关键步骤包括通过Lewis酸介导的[3.2.1]氧双环内酯裂解，非对映选择性内酯化，对映选择性酶酯水解和关键中间体与胸腺嘧啶的非对映选择性糖苷化，β选择性为100％。
• Synthesis of amino sugars through a highly diastereoselective dipolar cycloaddition. Enantioselective synthesis of the carbohydrate segment of Sch 38516
  作者：Zhongmin Xu、Charles W Johannes、Daniel S La、Gloria E Hofilena、Amir H Hoveyda

  DOI：10.1016/s0040-4020(97)01023-5

  日期：1997.12

  A concise and stereoselective route for the synthesis of the carbohydrate moiety of the antifungal agent Sch 38516 is described. The synthesis scheme includes a dipolar cycloaddition, which is rendered diastereoselective through the use of a readily available and easily removable chiral auxiliary.

  描述了用于合成抗真菌剂Sch 38516的碳水化合物部分的简明和立体选择性的途径。该合成方案包括偶极环加成，其通过使用容易获得且易于除去的手性助剂而成为非对映选择性的。
• Synthesis of β,γ-disubstituted-γ-lactones through a Johnson–Claisen rearrangement: a short route to xylobovide, nor-canadensolide, canadensolide, sporothriolide and santolinolide
  作者：Rodney A. Fernandes、Arun B. Ingle、Vijay P. Chavan

  DOI：10.1016/j.tetasy.2009.11.018

  日期：2009.12

  The Johnson-Claisen rearrangement of allyl alcohols with chiral vicinal diol functionality was employed to access chiral beta,gamma-disubstituted-gamma-lactones in high enantio- and diastereoselectivity. These were efficiently converted into nor-canadensolide, the advanced gamma-(lactone-lactol) intermediate for xylobovide, canadensolide and sporothriolide and the lactone moiety of the santolinolides. (C) 2009 Elsevier Ltd. All rights reserved.
• Enantioselective Total Synthesis of Antifungal Agent Sch 38516
  作者：Zhongmin Xu、Charles W. Johannes、Sarri S. Salman、Amir H. Hoveyda

  DOI：10.1021/ja9626603

  日期：1996.1.1
• De Novo Asymmetric Synthesis of Anamarine and Its Analogues
  作者：Dong Gao、George A. O'Doherty

  DOI：10.1021/jo051681p

  日期：2005.11.1

  The enantioselective synthesis of anamarine has been achieved in 21 steps. The route relies on enantio- and regioselective Sharpless dihydroxylation of dienoate ester and zinc borohydride reduction to establish the C-8-C-11 stereochemistry. A diastereoselective Leighton allylation established the desired C-5 stereochemistry. The route has also been used to prepare two diastereoisomers of anamarine in 14 steps.