(3Z,5S,6S,7R,8R,9S)-8-(tert-butyldimethylsilyloxy)-10-hydroxy-6-(triethylsilyloxy)-5,7,9-trimethyldeca-1,3-diene | 649755-88-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3Z,5S,6S,7R,8R,9S)-8-(tert-butyldimethylsilyloxy)-10-hydroxy-6-(triethylsilyloxy)-5,7,9-trimethyldeca-1,3-diene
• 英文别名: (Z)-(2S,3R,4R,5S,6S)-3-(tert-butyldimethylsilanyloxy)-2,4,6-trimethyl-5-triethylsilanyloxydeca-7,9-dien-1-ol；(Z)-(2S,3R,4R,5S,6S)-3-(tert-butyl-dimethyl-silanyloxy)-2,4,6-trimethyl-5-triethylsilanyloxy-deca-7,9-dien-1-ol；(2S,3R,4R,5S,6S,7Z)-3-[tert-butyl(dimethyl)silyl]oxy-2,4,6-trimethyl-5-triethylsilyloxydeca-7,9-dien-1-ol
• CAS: 649755-88-4
• 化学式: C₂₅H₅₂O₃Si₂
• 分子量: 456.857
• InChiKey: VMUDGOXNJDZEEW-AAACHIDTSA-N

物化性质

• 沸点：
  468.9±45.0 °C(Predicted)
• 密度：
  0.889±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.41
• 重原子数：
  30
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3Z,5S,6S,7R,8R,9S)-8-(tert-butyldimethylsilyloxy)-10-hydroxy-6-(triethylsilyloxy)-5,7,9-trimethyldeca-1,3-diene 在 咪唑 、 叔丁基锂 、 8-甲氧基-9-硼杂双环[3.3.1]壬烷 、 三苯基膦 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 水 、 乙腈 为溶剂， 反应 18.92h， 生成 (3Z,11Z)-(5S,6S,7S,8R,9S,13S,14R,15S)-8,14-bis-(tertbutyldimethylsilanyloxy)-5,7,9,11,13,15-hexamethyl-6,16-bis-triethylsilanyloxyhexadeca-1,3,11-triene
  参考文献：
  名称：

  A Formal Synthesis of (+)-Discodermolide

  摘要：

  Herein, we report the formal synthesis of (+)-discodermolide (1), a promising anticancer agent of sponge origin, in 24 linear steps, with 35 steps in total. The route proceeds from lactone 2, a building block containing the common 1,2-anti-2,3-syn stereotriad found in each of the three subunits, methyl ketone 4 (C-1-C-6), vinyl iodide 7 (C-9--C-14), and iodide 8 (C-15-C-24) utilized for the construction of L The key fragment union was achieved by a Suzuki cross-coupling between 7 and 8.

  DOI：

  10.1021/op049807s
• 作为产物：
  描述：

  (Z)-(2R,3S,4S)-2,4-dimethyl-3-triethylsilanyloxyocta-5,7-dienal 在 2,6-二甲基吡啶 、 锂硼氢 、 正丁基锂 、 三氟甲磺酸二丁硼 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 6.25h， 生成 (3Z,5S,6S,7R,8R,9S)-8-(tert-butyldimethylsilyloxy)-10-hydroxy-6-(triethylsilyloxy)-5,7,9-trimethyldeca-1,3-diene
  参考文献：
  名称：

  A Formal Synthesis of (+)-Discodermolide

  摘要：

  Herein, we report the formal synthesis of (+)-discodermolide (1), a promising anticancer agent of sponge origin, in 24 linear steps, with 35 steps in total. The route proceeds from lactone 2, a building block containing the common 1,2-anti-2,3-syn stereotriad found in each of the three subunits, methyl ketone 4 (C-1-C-6), vinyl iodide 7 (C-9--C-14), and iodide 8 (C-15-C-24) utilized for the construction of L The key fragment union was achieved by a Suzuki cross-coupling between 7 and 8.

  DOI：

  10.1021/op049807s

文献信息

• Total Synthesis of Discodermolide: Optimization of the Effective Synthetic Route
  作者：Elsa de Lemos、François-Hugues Porée、Arnaud Bourin、Julien Barbion、Evangelos Agouridas、Marie-Isabelle Lannou、Alain Commerçon、Jean-François Betzer、Ange Pancrazi、Janick Ardisson

  DOI：10.1002/chem.200801478

  日期：2008.12.8

  An efficient and modulable total synthesis of discodermolide (DDM), a unique marine anticancer polyketide is described including related alternative synthetic approaches. Particularly notable is the repeated application of a crotyltitanation reaction to yield homoallylic (Z)-O-ene-carbamate alcohols with excellent selectivity. Advantage was taken of this reaction not only for the stereocontrolled building

  一种高效，可调节的二甲蝶呤（DDM）的合成方法，一种独特的海洋抗癌聚酮化合物，包括相关的替代合成方法。尤其值得注意的是，重复进行crotyltitanate反应，以具有优异的选择性产生均烯丙基（Z）-O-烯-氨基甲酸酯醇。利用该反应不仅用于DDM的顺-反甲基-羟基-甲基三单元组的立体控制结构，而且还用于末端（Z）-二烯的直接结构。还特别感兴趣的是通过高度选择性的致各向异性重排来安装C13 = C14（Z）-双键。在两个连续阶段中制备中间C8-C14片段并将其与C1-C7部分偶联是一个真正的挑战，需要仔细优化。探索了几种合成路线以允许高和可靠的产量。由于这种方法的灵活性和鲁棒性，它可以实现DDM的系统结构变化，因此可以开发和探索新颖的discodermolide结构类似物。
• [EN] SYNTHESIS OF DISCODERMOLIDE<br/>[FR] SYNTHESE DU DISCODERMOLIDE
  申请人：NOVARTIS AG

  公开号：WO2004009574A1

  公开（公告）日：2004-01-29

  The invention relates to a process for preparing discodermolide, for preparing intermediates for the manufacture of discodermolide and discodermolide analogues and to the intermediates obtained during the process. Wherein the process proceeds via a tetraene of formula (IV).

  该发明涉及一种制备discodermolide的过程，用于制备制造discodermolide和discodermolide类似物的中间体，以及在过程中获得的中间体。其中，该过程通过式（IV）的四烯体进行。
• α-Oxygenated Crotyltitanium and Dyotropic Rearrangement in the Total Synthesis of Discodermolide
  作者：Elsa de Lemos、François-Hugues Porée、Alain Commerçon、Jean-François Betzer、Ange Pancrazi、Janick Ardisson

  DOI：10.1002/anie.200604629

  日期：2007.3.5
• Deconstruction−Reconstruction Strategy for Accessing Valuable Polyketides. Preparation of the C15−C24 Stereopentad of Discodermolide
  作者：Kathlyn A. Parker、Peng Wang

  DOI：10.1021/ol702144u

  日期：2007.11.1

  An advanced, known intermediate for discodermolide synthesis was prepared by an efficient sequence from the readily available fermentation product oleandomycin. The scheme makes use of a new method for the direct cleavage of aminoglycosides, a critical double-bond isomerization, and a selective protection of two of three hydroxyl groups in a modified oleandolide. This synthesis illustrates a new strategy, "deconstruction-reconstruction", for accessing stereochemically complex polyketide building blocks.
• A Formal Synthesis of (+)-Discodermolide
  作者：Olivier Loiseleur、Guido Koch、Jacques Cercus、Friedrich Schürch

  DOI：10.1021/op049807s

  日期：2005.5.1

  Herein, we report the formal synthesis of (+)-discodermolide (1), a promising anticancer agent of sponge origin, in 24 linear steps, with 35 steps in total. The route proceeds from lactone 2, a building block containing the common 1,2-anti-2,3-syn stereotriad found in each of the three subunits, methyl ketone 4 (C-1-C-6), vinyl iodide 7 (C-9--C-14), and iodide 8 (C-15-C-24) utilized for the construction of L The key fragment union was achieved by a Suzuki cross-coupling between 7 and 8.