methyl (E)-4-(tert-butyldimethylsiloxy)-2,4-pentadienoate | 174966-14-4

• 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: methyl (E)-4-(tert-butyldimethylsiloxy)-2,4-pentadienoate
• 英文别名: methyl (2E)-4-[tert-butyl(dimethyl)silyl]oxypenta-2,4-dienoate
• CAS: 174966-14-4
• 化学式: C₁₂H₂₂O₃Si
• 分子量: 242.39
• InChiKey: QWTAAAOWVGQXRJ-CMDGGOBGSA-N

物化性质

• 沸点：
  255.3±23.0 °C(Predicted)
• 密度：
  0.929±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (E)-4-(tert-butyldimethylsiloxy)-2,4-pentadienoate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 以91%的产率得到(E)-4-(tert-butyldimethylsiloxy)-2,4-pentadien-1-ol
  参考文献：
  名称：

  双环[4.4.0]癸烯骨架天然产物合成的研究：合成和未催化分子内Diels-Alder反应的癸三烯酮底物

  摘要：

  以烯酮 7 和 8 为原料合成了甲硅烷氧基二烯 9 和 12。环丙烷化和随后用山梨基溴进行烷基化以良好的整体效率提供四取代的甲硅烷氧基环丙烷 15 和 16。它们用氟化物试剂进行环裂解得到 1,7,9-癸三烯酮 5 和 17；后者转化为受保护的化合物 6。将 5 和 6 的分子内 Diels-Alder 热反应与相关的三烯酮 3 和 4 的热分子内反应进行比较。八酮 1、2、21 和 22 作为三种或四种非对映体的混合物形成. 因此，对于天然产物的立体选择性构建，例如 α-eudesmol 或 dihydromevinolin，必须开发用于环加成步骤的替代反应条件。

  DOI：

  10.1002/(sici)1099-0690(199906)1999:6<1377::aid-ejoc1377>3.0.co;2-l
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 、 反-4-氧-2-戊烯酸甲酯 在 三乙胺 、 sodium iodide 作用下， 以 乙腈 为溶剂， 反应 72.0h， 以73%的产率得到methyl (E)-4-(tert-butyldimethylsiloxy)-2,4-pentadienoate
  参考文献：
  名称：

  双环[4.4.0]癸烯骨架天然产物合成的研究：合成和未催化分子内Diels-Alder反应的癸三烯酮底物

  摘要：

  以烯酮 7 和 8 为原料合成了甲硅烷氧基二烯 9 和 12。环丙烷化和随后用山梨基溴进行烷基化以良好的整体效率提供四取代的甲硅烷氧基环丙烷 15 和 16。它们用氟化物试剂进行环裂解得到 1,7,9-癸三烯酮 5 和 17；后者转化为受保护的化合物 6。将 5 和 6 的分子内 Diels-Alder 热反应与相关的三烯酮 3 和 4 的热分子内反应进行比较。八酮 1、2、21 和 22 作为三种或四种非对映体的混合物形成. 因此，对于天然产物的立体选择性构建，例如 α-eudesmol 或 dihydromevinolin，必须开发用于环加成步骤的替代反应条件。

  DOI：

  10.1002/(sici)1099-0690(199906)1999:6<1377::aid-ejoc1377>3.0.co;2-l

文献信息

• New Surprises with Fischer Carbene Complexes: Formal[3+2] Cycloadditions with and without Preeceding Carben–Ligand Matathesis
  作者：Matthias Hoffmann、Hans-Ulrich Reissig、Matthias Buchert

  DOI：10.1002/anie.199702831

  日期：1997.2.14
• Reactions of Fischer Carbene Complexes with Siloxydienes: Formation of Cycloheptadiene and Cyclopentene Derivatives—Formal [2+1] Cycloaddition Followed by Cope Rearrangement Versus Formal [3+2] Cycloaddition with or without Preceding Carbene-Ligand Metathesis
  作者：Matthias Hoffmann、Matthias Buchert、Hans-Ulrich Reißig

  DOI：10.1002/(sici)1521-3765(19990301)5:3<876::aid-chem876>3.0.co;2-t

  日期：1999.3.1

  Thermal reactions of the alpha,beta-unsaturated Fischer carbene complexes 3-5 with the siloxydienes 6 and 7 mainly furnished the expected cyclohepta-1,4-dienes such as 9, 10, 12, 14, and 15, whose formation is explained by a formal [2+1] cycloaddition followed by Cope rearrangement. The rather electron-rich carbene complex 5 also afforded the cyclopentene derivatives II and 16 as by-products, which are probably formed by two distinct mechanisms. Single diastereomers of the cyclopentene derivatives 17 and 18 were isolated as the exclusive products of the reactions of 3 and 4, respectively, with the donor/acceptor-substituted 1,3-diene 8. This process is interpreted as a metalla Diels-Alder reaction to form a chromacyclohexene intermediate 25, which subsequently undergoes fragmentation to give cyclopentene derivatives with the required constitution. Most surprisingly, the reactions of simple carbene complexes 1 or 2 with the siloxydienes 7 or 8 yielded cyclopentene derivatives 19 and 20 that do not contain the carbene ligand of the precursor complexes. Instead, the constitution of the isolated products can be accounted for by a formal diene dimerization with fragmentation of a methylene unit. Their formation can be interpreted by an unprecedented sequence of carbene-ligand metathesis followed by a metalla Diels-Alder reaction and reductive fragmentation. All these results illustrate the great importance of electronic fine-tuning in the precursors involved in reactions of Fischer carbene complexes with 1,S-dienes.
• [EN] MULTICYCLIC COMPOUNDS<br/>[FR] COMPOSÉS MULTICYCLIQUES
  申请人：[en]ATLEE BIOTECH, INC.

  公开号：WO2023086580A2

  公开（公告）日：2023-05-19

  Compounds of Formulae (I), (II) and (III), including pharmaceutically acceptable salts are described herein. Such compounds, as well as pharmaceutically acceptable salts and compositions thereof, are useful for treating diseases or conditions a disease or disorder that can be treated with a KOR agonist and/or MOR agonist. Compounds described herein, along with pharmaceutically acceptable salts and compositions thereof, can be used to alleviate at least one symptom of the disease or disorder described herein.
• Studies on the Synthesis of Natural Products with Bicyclo[4.4.0]decene Skeleton: Synthesis and Uncatalysed Intramolecular Diels–Alder Reactions of the Decatrienone Substrates
  作者：Barbara Frey、Jürgen Schnaubelt、Hans-Ulrich Reißig

  DOI：10.1002/(sici)1099-0690(199906)1999:6<1377::aid-ejoc1377>3.0.co;2-l

  日期：1999.6

  synthesized. Cyclopropanation and subsequent alkylation with sorbyl bromide provided tetrasubstituted siloxycyclopropanes 15 and 16 in good overall efficiency. Their ring cleavage with fluoride reagents gave 1,7,9-decatrienones 5 and 17; the latter was converted into the protected compound 6. The thermal intramolecular Diels–Alder reactions of 5 and 6 were compared with those of related trienones 3 and

  以烯酮 7 和 8 为原料合成了甲硅烷氧基二烯 9 和 12。环丙烷化和随后用山梨基溴进行烷基化以良好的整体效率提供四取代的甲硅烷氧基环丙烷 15 和 16。它们用氟化物试剂进行环裂解得到 1,7,9-癸三烯酮 5 和 17；后者转化为受保护的化合物 6。将 5 和 6 的分子内 Diels-Alder 热反应与相关的三烯酮 3 和 4 的热分子内反应进行比较。八酮 1、2、21 和 22 作为三种或四种非对映体的混合物形成. 因此，对于天然产物的立体选择性构建，例如 α-eudesmol 或 dihydromevinolin，必须开发用于环加成步骤的替代反应条件。