(E)-4-(tert-butyl-diphenyl-silanyloxy)-but-2-enethioic acid S-ethyl ester | 917590-73-9

• 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)-4-(tert-butyl-diphenyl-silanyloxy)-but-2-enethioic acid S-ethyl ester
• 英文别名: S-ethyl (E)-4-[tert-butyl(diphenyl)silyl]oxybut-2-enethioate
• CAS: 917590-73-9
• 化学式: C₂₂H₂₈O₂SSi
• 分子量: 384.615
• InChiKey: MWLYZYTVLMVMIC-SFQUDFHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-4-(tert-butyl-diphenyl-silanyloxy)-but-2-enethioic acid S-ethyl ester 在 palladium on activated charcoal 吡啶 、 三乙基硅烷 、 二异丁基氢化铝 、 magnesium 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 313.19h， 生成 (-)-(2S,4S,6S,8S,10S,12S,14S)-tert-butyl-(2,4,6,8,10,12,14-heptamethyl-triacontyloxy)-diphenyl-silane
  参考文献：
  名称：

  Catalytic Asymmetric Synthesis of Phthioceranic Acid, a Heptamethyl-Branched Acid from Mycobacterium tuberculosis

  摘要：

  The first total synthesis of phthioceranic acid (1) has been achieved by an iterative catalytic asymmetric 1,4-addition protocol. This method provides a robust and high-yielding route for the preparation of 1,3-oligomethyl (deoxypropionate) arrays. After the desired number of methyl groups has been introduced, these arrays can be further functionalized at both ends to polymethyl-substituted lipids such as phthioceranic acid, a heptamethyl-branched fatty acid from the virulence factor Sulfolipid-I (2), found in Mycobacterium tuberculosis.

  DOI：

  10.1021/ol071078o
• 作为产物：
  描述：

  叔丁基二苯基氯硅烷 在 咪唑 、 2-碘酰基苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 72.0h， 生成 (E)-4-(tert-butyl-diphenyl-silanyloxy)-but-2-enethioic acid S-ethyl ester
  参考文献：
  名称：

  Catalytic asymmetric synthesis of mycocerosic acid

  摘要：

  首次实现了麦角甾酸的不对称全合成，通过运用迭代的手性选择性1,4-加成反应，实现了对1,3-多甲基序列的高效构建与完全立体控制；并通过合成长链四甲基癸酸——灰雁（Anser anser）尾脂腺蜡的组分之一——进一步证实了其应用。

  DOI：

  10.1039/b612593j

文献信息

• Formal Synthesis of the Anti-Angiogenic Polyketide (−)-Borrelidin under Asymmetric Catalytic Control
  作者：Ashoka V. R. Madduri、Adriaan J. Minnaard

  DOI：10.1002/chem.201001284

  日期：——

  potent anti‐angiogenesis activity. This paper describes its formal total synthesis by the most efficient route to date. This modular approach takes optimal benefit of asymmetric catalysis and permits the synthesis of analogues; in addition, the high yields and selectivities obtained eliminate the need for separation of stereoisomers. The upper half of borrelidin has been accessed by iterative copper‐catalysed

  硼瑞林（1）是一种聚酮化合物，具有极强的抗血管生成活性。本文通过迄今为止最有效的方法描述了其正式的全合成方法。这种模块化方法利用了不对称催化的最佳优势，并允许合成类似物。另外，获得的高产率和选择性消除了分离立体异构体的需要。硼氢化利丁的上半部分已通过铜催化的甲基溴的不对称共轭铜的迭代添加而获得，而分子下半部分的合成是通过不对称加氢和交叉甲基化作为关键步骤而实现的。
• Catalytic asymmetric synthesis of mycocerosic acid
  作者：Bjorn ter Horst、Ben L. Feringa、Adriaan J. Minnaard

  DOI：10.1039/b612593j

  日期：——

  The first catalytic asymmetric total synthesis of mycocerosic acid was achieved via the application of iterative enantioselective 1,4-addition reactions and allows for the efficient construction of 1,3-polymethyl arrays with full stereocontrol; further exemplified by the synthesis of tetramethyl-decanoic acid, a component of the preen-gland wax of the graylag goose, Anser anser.

  首次实现了麦角甾酸的不对称全合成，通过运用迭代的手性选择性1,4-加成反应，实现了对1,3-多甲基序列的高效构建与完全立体控制；并通过合成长链四甲基癸酸——灰雁（Anser anser）尾脂腺蜡的组分之一——进一步证实了其应用。
• Catalytic Asymmetric Synthesis of Mycolipenic and Mycolipanolic Acid
  作者：Bjorn ter Horst、Jeroen van Wermeskerken、Ben L. Feringa、Adriaan J. Minnaard

  DOI：10.1002/ejoc.200901120

  日期：2010.1

  The first asymmetric synthesis of mycolipenic acid and mycolipanolic acid by using an improved iterative procedure involving catalytic asymmetric conjugate addition of MeMgBr as the key step is described. Mycolipenic and mycolipanolic acid are obtained in 11 steps with perfect stereocontrol, and both acids are identical to their counterparts from natural sources.

  描述了通过使用改进的迭代程序，包括 MeMgBr 的催化不对称共轭加成作为关键步骤，首次不对称合成霉烯酸和霉烯酸。Mycolipenic 和 mycolipanolic 酸是通过 11 个步骤获得的，具有完美的立体控制，这两种酸与来自天然来源的对应物相同。
• Highly Versatile Enantioselective Conjugate Addition of Grignard Reagents to α,β-Unsaturated Thioesters
  作者：Beatriz Maciá Ruiz、Koen Geurts、M. Ángeles Fernández-Ibáñez、Bjorn ter Horst、Adriaan J. Minnaard、Ben L. Feringa

  DOI：10.1021/ol702425a

  日期：2007.11.1

  for the asymmetric copper-catalyzed conjugate addition of Grignard reagents to alpha,beta-unsaturated thioesters. MeMgBr adds to aromatic alpha,beta-unsaturated thioesters with excellent enantioselectivities and moderate to good yields using Josiphos/CuBr and Tol-BINAP/CuI complexes. The use of bulky Grignard reagents leads to unprecedented enantioselectivities in the 1,4-addition to a broad range

  在这里，我们报告了格氏试剂到α，β-不饱和硫代酯的不对称铜催化共轭加成反应的有效催化剂。使用Josiphos / CuBr和Tol-BINAP / CuI配合物，MeMgBr添加到芳族α，β-不饱和硫酯中，具有出色的对映选择性和中等至良好的收率。使用Tol-BINAP / CuI在大范围的芳族和脂族α，β-不饱和硫酯的1,4-加成反应中，使用笨重的格氏试剂会导致空前的对映选择性。使用Tol-BINAP / CuI可以实现目前为止报道的将格氏试剂添加到拥挤的β-取代的脂肪族底物中的最高对映选择性。
• Catalytic Asymmetric Synthesis of Phthioceranic Acid, a Heptamethyl-Branched Acid from <i>Mycobacterium tuberculosis</i>
  作者：Bjorn ter Horst、Ben L. Feringa、Adriaan J. Minnaard

  DOI：10.1021/ol071078o

  日期：2007.8.1

  The first total synthesis of phthioceranic acid (1) has been achieved by an iterative catalytic asymmetric 1,4-addition protocol. This method provides a robust and high-yielding route for the preparation of 1,3-oligomethyl (deoxypropionate) arrays. After the desired number of methyl groups has been introduced, these arrays can be further functionalized at both ends to polymethyl-substituted lipids such as phthioceranic acid, a heptamethyl-branched fatty acid from the virulence factor Sulfolipid-I (2), found in Mycobacterium tuberculosis.