ethyl 5-((tert-butyldiphenylsilyl)oxy)pentanoate | 1254568-93-8

• 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: ethyl 5-((tert-butyldiphenylsilyl)oxy)pentanoate
• 英文别名: Ethyl 5-[tert-butyl(diphenyl)silyl]oxypentanoate；ethyl 5-[tert-butyl(diphenyl)silyl]oxypentanoate
• CAS: 1254568-93-8
• 化学式: C₂₃H₃₂O₃Si
• 分子量: 384.591
• InChiKey: UIONPSNRAXYFGN-UHFFFAOYSA-N

物化性质

• 沸点：
  428.4±37.0 °C(predicted)
• 密度：
  1.02±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  ethyl 5-((tert-butyldiphenylsilyl)oxy)pentanoate 在 正丁基锂 、 二异丙胺 、 碘 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以91 %的产率得到ethyl 5-((tert-butyldiphenylsilyl)oxy)-2-iodopentanoate
  参考文献：
  名称：

  非对映选择性、路易斯酸介导的联烯酸衍生物和 1,3-环戊二烯的 Diels-Alder 反应

  摘要：

  在其末端碳原子上具有不同取代基的丙二烯显示出轴向手性，并且可以通过光化学去外消旋化方案以对映体纯形式获得。现在已经研究了联烯酸衍生物在什么条件下与 1,3-环戊二烯发生 Diels-Alder 反应以及产生哪些产物。环状衍生物（内酰胺、内酯）经历由路易斯酸 Eu(fod) 3催化的外向选择性反应，而无环衍生物高度优先地产生内向产物 (EtAlCl 2作为优选的路易斯酸）。环外双键形成，具有出色的非对映选择性，手性转移接近完美。将该方法应用于倍半萜类β-檀香醇( 1 )和10( E )-β-檀香酸( 13 )的合成。

  DOI：

  10.1039/d3ob00598d
• 作为产物：
  描述：

  delta-戊内酯 在 咪唑 、 sodium hydroxide 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 170.5h， 生成 ethyl 5-((tert-butyldiphenylsilyl)oxy)pentanoate
  参考文献：
  名称：

  Lipase-mediated regioselective modifications of macrolactonic sophorolipids

  摘要：

  Chemoenzymatic synthesis and modification of well-defined macrolactonic sophorolipid (SLML) analogues via a series of successive regioselective de-esterification/transesterification reactions is investigated. Of the lipases screened, Candida antartica lipase- B (Novozyme-435) successfully deacylated the C-6' acetoxy group of natural and peracylated SLMLs. Subsequent transesterification with acylating agents (esters of fatty acids) was successful only with the C-6' deacetylated natural SLML providing an avenue to well-defined analogues of varying amphilicity. The macrolactonic motif was essential for enzymatic recognition of the sophorose rings of these complex glycolipids. In the absence of the lactonic motif, the peracylated sophorose rings are not deacylated, rather the carboxyl end of the non-lactonic forms that was preferentially transesterified. All macrolactonic derivatives were characterized by IR, H-1, C-13, H-1-H-1 and H-1-C-13 NMR spectroscopy, as well as HRMS where applicable. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2017.02.043

文献信息

• Synthetic studies toward Swinhoeisterol A: Synthesis of the 6/6/5/7 tetracyclic core
  作者：Volha V. Kazlova、Alaksiej L. Hurski

  DOI：10.1016/j.tetlet.2023.154840

  日期：2024.1

  6/6/5/7 Tetracyclic core of Swinhoeisterol A was constructed starting from Wieland-Miescher ketone and silylated ethyl 5–hydroxyvalerate. After modification, the bicyclic and linear subunits were assembled by means of cross-metathesis reaction. Then, cyclopentane C ring was formed by the intramolecular aldol condensation. C17-stereocenter was constructed using Claisen rearrangement followed by the

  6/6/5/7 Swinhoeisterol A 的四环核心是从 Wieland-Miescher 酮和甲硅烷基化 5-羟基戊酸乙酯开始构建的。修饰后，通过交叉复分解反应组装双环和线性亚基。然后，通过分子内羟醛缩合形成环戊烷C环。C17-立体中心是使用克莱森重排和脱羰步骤构建的。最后，应用烯反应同时形成环庚烷D环和B环和C环之间的四取代双键。
• Construction of a fully substituted cyclopentenone as the core skeleton of stemonamide via a Nazarov cyclization
  作者：Kentaro Yaji、Mitsuru Shindo

  DOI：10.1016/j.tetlet.2010.08.032

  日期：2010.10

  A synthetic study of the Stemona alkaloid stemonamide is described. The FeCl(3)-promoted fast Nazarov reaction of beta-alkoxy divinyl ketones in the presence of t-BuOH afforded an alpha-methylene cyclopentenone, which was subsequently subjected to the Rh-catalyzed C-H amination to provide a fully appropriately substituted alpha-methylene cyclopentenone as the core skeleton of stemonamide. (C) 2010 Elsevier Ltd. All rights reserved.
• Lipase-mediated regioselective modifications of macrolactonic sophorolipids
  作者：Aliya Sembayeva、Beniam Berhane、Jason A. Carr

  DOI：10.1016/j.tet.2017.02.043

  日期：2017.4

  Chemoenzymatic synthesis and modification of well-defined macrolactonic sophorolipid (SLML) analogues via a series of successive regioselective de-esterification/transesterification reactions is investigated. Of the lipases screened, Candida antartica lipase- B (Novozyme-435) successfully deacylated the C-6' acetoxy group of natural and peracylated SLMLs. Subsequent transesterification with acylating agents (esters of fatty acids) was successful only with the C-6' deacetylated natural SLML providing an avenue to well-defined analogues of varying amphilicity. The macrolactonic motif was essential for enzymatic recognition of the sophorose rings of these complex glycolipids. In the absence of the lactonic motif, the peracylated sophorose rings are not deacylated, rather the carboxyl end of the non-lactonic forms that was preferentially transesterified. All macrolactonic derivatives were characterized by IR, H-1, C-13, H-1-H-1 and H-1-C-13 NMR spectroscopy, as well as HRMS where applicable. (C) 2017 Elsevier Ltd. All rights reserved.
• Diastereoselective, Lewis acid-mediated Diels–Alder reactions of allenoic acid derivatives and 1,3-cyclopentadienes
  作者：Freya M. Harvey、Alexandra H. Heidecker、Christian Merten、Thorsten Bach

  DOI：10.1039/d3ob00598d

  日期：——

  conditions allenoic acid derivatives undergo a Diels–Alder reaction with 1,3-cyclopentadienes and which products result. Cyclic derivatives (lactams, lactones) underwent an exo-selective reaction catalyzed by the Lewis acid Eu(fod)3, while acyclic derivatives yielded with high preference the endo-products (EtAlCl2 as the preferred Lewis acid). The exocyclic double bond forms with exquisite diastereoselectivity

  在其末端碳原子上具有不同取代基的丙二烯显示出轴向手性，并且可以通过光化学去外消旋化方案以对映体纯形式获得。现在已经研究了联烯酸衍生物在什么条件下与 1,3-环戊二烯发生 Diels-Alder 反应以及产生哪些产物。环状衍生物（内酰胺、内酯）经历由路易斯酸 Eu(fod) 3催化的外向选择性反应，而无环衍生物高度优先地产生内向产物 (EtAlCl 2作为优选的路易斯酸）。环外双键形成，具有出色的非对映选择性，手性转移接近完美。将该方法应用于倍半萜类β-檀香醇( 1 )和10( E )-β-檀香酸( 13 )的合成。