(E)-methyl-6-[(tetrahydro-2H-pyran-2-yl)oxy]-hex-2-en-oate | 127089-43-4

• 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)-methyl-6-[(tetrahydro-2H-pyran-2-yl)oxy]-hex-2-en-oate
• 英文别名: methyl (E)-6-(oxan-2-yloxy)hex-2-enoate
• CAS: 127089-43-4
• 化学式: C₁₂H₂₀O₄
• 分子量: 228.288
• InChiKey: MXYKHVMAQDDEBF-XVNBXDOJSA-N

物化性质

• 沸点：
  330.2±42.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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)-methyl-6-[(tetrahydro-2H-pyran-2-yl)oxy]-hex-2-en-oate 在 manganese(IV) oxide 、 正丁基锂 、 camphor-10-sulfonic acid 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 40.67h， 生成 (4E)-hepta-4,6-dien-1-ol
  参考文献：
  名称：

  内部取代的三烯基砜的分子内Diels-Alder反应。具有桥头磺酰基的双环[4.3.0]和-[4.4.0]体系的合成

  摘要：

  一系列具有内部活化的乙烯基砜二亲核基团的三烯经过分子内Diels-Alder（IMDA）反应，对顺式融合产物具有高或完全选择性。在连接二烯和亲二烯体的碳系链中并入甲硅烷氧基基团会增加IMDA反应性。这些方法的立体化学结果根据对外向性苯基磺酰基的偏爱以及使甲硅烷氧基和砜取代基之间的未键合相互作用最小化而合理化。

  DOI：

  10.1016/0040-4020(94)01045-2
• 作为产物：
  描述：

  4-四氢吡喃基氧基-丁烷-1-醇 在 sodium acetate 、 potassium carbonate 、 pyridinium chlorochromate 作用下， 生成 (E)-methyl-6-[(tetrahydro-2H-pyran-2-yl)oxy]-hex-2-en-oate
  参考文献：
  名称：

  ikarugamycin的合成：新的环C封闭策略的模型研究

  摘要：

  通过精制已被转化为天然产物的环戊烷类似物的反式-双取代的环戊烷，证明了适用于卡他霉素的C环封闭的新的共轭加成-烷基化方法。

  DOI：

  10.1016/s0040-4039(00)89067-x

文献信息

• Synthesis of ikarugamycin: Model studies on a new strategy for the closure of ring C
  作者：Raymond C.F. Jones、Richard F. Jones

  DOI：10.1016/s0040-4039(00)89067-x

  日期：1990.1

  A new conjugate addition-alkylation approach suitable for the closure of ring C of ikarugamycin is demonstrated by the concise elaboration of a trans-disubstituted cyclopentane that has been converted into the cyclopentane analogue of the natural product.

  通过精制已被转化为天然产物的环戊烷类似物的反式-双取代的环戊烷，证明了适用于卡他霉素的C环封闭的新的共轭加成-烷基化方法。
• Stereocontrolled Synthesis of Cyclic Ethers by Intramolecular Hetero-Michael Addition. 5. Synthesis of All Diastereoisomers of 2,3,5,6-Tetrasubstituted Tetrahydropyrans
  作者：Juan M. Betancort、Víctor S. Martín、José M. Padrón、José M. Palazón、Miguel A. Ramírez、Marcos A. Soler

  DOI：10.1021/jo9619241

  日期：1997.7.1

  A systematic approach to the enantiomeric synthesis of all possible diastereoisomers of 2,6-dialkyl-3,5-dioxytetrahydropyrans is described. The key step in the described methodology is the intramolecular cyclization of enantiomerically enriched (greater than or equal to 95% ee) 7-hydroxy-4-(benzoyloxy)-2,3-unsaturated esters. Infused systems, six of the eight diastereoisomers for one enantiomeric series were synthesized using this procedure as a key step. Using those with the suitable stereochemistry, the two left were synthesized by simple chemical transformations: in one case by the basic isomerization of the carbon with the (methoxycarbonyl)methyl substituent or by a Mitsunobu inversion of a secondary alcohol available from the benzoyloxy group,in the remaining one by a consecutive sequence of oxidation and reduction reactions again over the free secondary alcohol. The stereochemistry of the intramolecular hetero-Michael addition leading to 2,3-disubstituted tetrahydropyrans is highly predictable when kinetic conditions (low temperature and sodium or potassium bases) are used and can be rationalized by invoking a model of a chair-like transition state in which the benzoyloxy group is located in the equatorial mode and the stereochemical course of the approach of the alpha,beta-unsaturated ester is controlled by the geometry of the double bond. As a rule of thumb, the cyclization using E double bonds yielded cis-2,3-disubstituted tetrahydropyrans, while (Z)-unsaturated esters yielded the trans compounds. This empirical rule is followed in highly substituted systems, leading to fused 2,3,5,6-tetrasubstituted tetrahydropyrans, with the same absolute configuration in the carbon where the nucleophilic oxygen is located and the one where the benzoyloxy group is located. Those systems having opposite configurations yield the same trans-2,3-disubstituted compound. The isomerization under thermodynamic conditions (room or higher temperature with excess of base) of the diastereoisomers with the (methoxycarbonyl)methyl substituent in the axial mode led quantitatively to those in which such a group was located equatorially. The scope and limitations of the method are described in both the synthesis of the unsaturated precursor and the stereochemistry reached in the cyclization step.
• Enantiomeric synthesis of endo-substituted tetrahydropyrans
  作者：Victor S Martín、Maria T Nuñez、Miguel A Ramirez、Marcos A Soler

  DOI：10.1016/s0040-4039(00)94623-9

  日期：1990.1
• Sharma, G. V. M.; Rajagopal, D.; Sreenivasa Rao, E., Synthetic Communications, 1989, vol. 19, # 18, p. 3181 - 3190
  作者：Sharma, G. V. M.、Rajagopal, D.、Sreenivasa Rao, E.

  DOI：——

  日期：——
• SHARMA, G. V. M.;RAJAGOPAL, D.;SREENIVASA, E. RAO, SYNTH. COMMUN., 19,(1989) N8, C. 3181-3189
  作者：SHARMA, G. V. M.、RAJAGOPAL, D.、SREENIVASA, E. RAO

  DOI：——

  日期：——