(E)-(4R,5R)-methyl 5-(tert-butyldimethylsilyloxy)-4-hydroxy-2,6-heptadienoate | 1107608-15-0

• 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)-(4R,5R)-methyl 5-(tert-butyldimethylsilyloxy)-4-hydroxy-2,6-heptadienoate
• 英文别名: (4R,5R,E)-methyl 5-(tert-butyldimethylsilyloxy)-4-hydroxyhepta-2,6-dienoate；methyl (2E,4R,5R)-5-[tert-butyl(dimethyl)silyl]oxy-4-hydroxyhepta-2,6-dienoate
• CAS: 1107608-15-0
• 化学式: C₁₄H₂₆O₄Si
• 分子量: 286.444
• InChiKey: SYHBEZFUHVFRKZ-CZHKVUGUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.65
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-(4R,5R)-methyl 5-(tert-butyldimethylsilyloxy)-4-hydroxy-2,6-heptadienoate 在 1,2-双(二苯基膦基)苯 、 copper(II) acetate monohydrate 、 二异丁基氢化铝 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 环己烷 、 甲苯 、 叔丁醇 为溶剂， 反应 601.33h， 生成 (2R,5R,6R)-6-(tert-butyldimethylsilyloxy)-5-(methoxymethoxy)oct-7-en-2-yl acetate
  参考文献：
  名称：

  Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C₂-symmetric building block: a strategy for the synthesis of decanolide natural products

  摘要：

  从方便获取的外源手性池构建块（R,R）-己二烯-3,4-二醇出发，利用双向烯烃交换反应合成了十元环内酯stagonolide E和curvulide A。关键步骤包括：（i）位选择性交叉烯烃交换反应，（ii）高对映选择性的延伸挂链环烯烃闭环反应，形成（Z,E）构型的二烯基羧酸，以及（iii）Ru-脂肪酶催化的动力学拆分反应，在C9位建立所需的构型。环闭合通过大环内酯化实现。通过Sharpless环氧化反应，从stagonolide E合成了curvulide A。

  DOI：

  10.3762/bjoc.9.289
• 作为产物：
  描述：

  丙烯酸甲酯（MA） 、 (3R,4R)-4-((tert-butyldimethylsilyl)oxy)hexa-1,5-dien-3-ol 在 [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[[2-(1-methyl-2-oxopropoxy)phenyl]methylene]ruthenium(II) 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以90%的产率得到(E)-(4R,5R)-methyl 5-(tert-butyldimethylsilyloxy)-4-hydroxy-2,6-heptadienoate
  参考文献：
  名称：

  Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C₂-symmetric building block: a strategy for the synthesis of decanolide natural products

  摘要：

  从方便获取的外源手性池构建块（R,R）-己二烯-3,4-二醇出发，利用双向烯烃交换反应合成了十元环内酯stagonolide E和curvulide A。关键步骤包括：（i）位选择性交叉烯烃交换反应，（ii）高对映选择性的延伸挂链环烯烃闭环反应，形成（Z,E）构型的二烯基羧酸，以及（iii）Ru-脂肪酶催化的动力学拆分反应，在C9位建立所需的构型。环闭合通过大环内酯化实现。通过Sharpless环氧化反应，从stagonolide E合成了curvulide A。

  DOI：

  10.3762/bjoc.9.289

文献信息

• Synthesis and stereochemical assignment of (+)-Cladospolide D
  作者：Ke-Jhen Lu、Chia-Hsiu Chen、Duen-Ren Hou

  DOI：10.1016/j.tet.2008.10.059

  日期：2009.1

  Cladospolides A-D are 12-membered, alpha,beta-unsaturated lactones isolated from various species of Cladosporium. Cladospolide D is unique in its gamma-keto functionality and possesses antifungal activity; however, the stereochemistry of Cladoapolide D was unknown. We report the asymmetric syntheses to generate both possible diastereomers of Cladospolide D. Two regioselective cross-metatheses were applied to form the carbon skeleton, and the two olefins were differentiated by Michael addition, hydrogenation, and elimination. Later, the macrocycle was achieved through the Yamaguchi protocol. After comparing the spectroscopic data of the synthetic Cladospolide D with the reported values, the stereochemistry of Cladospolide D is confirmed as (2E,5R,11S). (C) 2008 Elsevier Ltd. All rights reserved.
• Bidirectional cross metathesis and ring-closing metathesis/ring opening of a <i>C</i>₂-symmetric building block: a strategy for the synthesis of decanolide natural products
  作者：Bernd Schmidt、Oliver Kunz

  DOI：10.3762/bjoc.9.289

  日期：——

  Starting from the conveniently available ex-chiral pool building block (R,R)-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i) a site-selective cross metathesis, (ii) a highly diastereoselective extended tethered RCM to furnish a (Z,E)-configured dienyl carboxylic acid and (iii) a Ru–lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

  从方便获取的外源手性池构建块（R,R）-己二烯-3,4-二醇出发，利用双向烯烃交换反应合成了十元环内酯stagonolide E和curvulide A。关键步骤包括：（i）位选择性交叉烯烃交换反应，（ii）高对映选择性的延伸挂链环烯烃闭环反应，形成（Z,E）构型的二烯基羧酸，以及（iii）Ru-脂肪酶催化的动力学拆分反应，在C9位建立所需的构型。环闭合通过大环内酯化实现。通过Sharpless环氧化反应，从stagonolide E合成了curvulide A。