(S,E)-4-((tert-butyldimethylsilyl)oxy)pent-2-en-1-al | 260978-54-9

• 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: (S,E)-4-((tert-butyldimethylsilyl)oxy)pent-2-en-1-al
• 英文别名: (S,E)-4-((tert-butyldimethylsilyl)oxy)pent-2-enal；(4S,2E)-4-tert-Butyldimethylsilyloxypent-2-enal；(4S,2E)-4-tert-butyldimethylsilyloxy-2-pentenal；(S)-4-(TBDMSO)-2-pentenal；(E,4S)-4-[tert-butyl(dimethyl)silyl]oxypent-2-enal
• CAS: 260978-54-9
• 化学式: C₁₁H₂₂O₂Si
• 分子量: 214.38
• InChiKey: MFEMTJAKNSWHBJ-JARNTUPDSA-N

物化性质

• 沸点：
  255.6±23.0 °C(Predicted)
• 密度：
  0.880±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.15
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S,E)-4-((tert-butyldimethylsilyl)oxy)pent-2-en-1-al 在 四丁基氟化铵 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 3.5h， 生成 2-[(3S,1E)-3-Hydroxybut-1-enyl]-1,3-dioxolane
  参考文献：
  名称：

  Stereoselective synthesis of allylic amines by rearrangement of allylic trifluoroacetimidates: stereoselective synthesis of polyoxamic acid and derivatives of other α-amino acids

  摘要：

  在甲苯中回流加热时，烯丙基三氟乙亚胺酸酯会发生[3,3] σ迁移重排，生成区域异构的烯丙基三氟乙酰胺。例如，三氟乙亚胺酸酯16和73重排生成三氟乙酰胺17和74，这些被用于合成聚氧基酸1的选择性合成中，以及三氟乙亚胺酸酯26的重排。这一重排是对映选择性合成(S)-和(R)-缬氨酸类似物37和48的关键步骤。其他例子包括由香叶醇、肉桂醇和苏儿醇分别制备的三氟乙亚胺酸酯52、54和56的重排，以及更复杂的三氟乙亚胺酸酯62和69的重排。这些重排的立体选择性比类似的烯丙基三氯乙亚胺酸酯重排稍快，与椅式六元过渡态结构的参与相符。

  DOI：

  10.1039/a905772b
• 作为产物：
  描述：

  (S,E)-ethyl 4-((tert-butyldimethylsilyl)oxy)pent-2-enoate 在 草酰氯 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 作用下， 生成 (S,E)-4-((tert-butyldimethylsilyl)oxy)pent-2-en-1-al
  参考文献：
  名称：

  Conformational Studies of Chiral .alpha.,.beta.-Unsaturated Aldehydes

  摘要：

  The conformational profiles for chiral alpha,beta-unsaturated aldehydes have been studied by a combination of ab initio MO methods and the variable-temperature MMR technique. The s-trans rotational isomer around the C-sp2-C-sp2 single bond is more stable than the s-cis conformer by similar to 500 cal/mol in chloroform. This difference is 950 cal/mol according to ab initio calculations at the MP2/6-31G* level of theory. The silyl ethers, 3a-d, prefer the C-O eclipsed form while the methyl ethers, 6a-d, favor the C-H eclipsed conformation for rotations around the C-sp3-C-sp2 bond.

  DOI：

  10.1021/jo00094a043

文献信息

• Oxidation of allylic and benzylic alcohols to aldehydes and carboxylic acids
  作者：Daniel Könning、Tobias Olbrisch、Fanni D. Sypaseuth、C. Christoph Tzschucke、Mathias Christmann

  DOI：10.1039/c4cc01305k

  日期：——

  An oxidation of allylic and benzylic alcohols to the corresponding carboxylic acids is effected by merging a Cu-catalyzed oxidation using O2 as a terminal oxidant with a subsequent chlorite oxidation (Lindgren oxidation). The protocol was optimized to obtain pure products without chromatography or crystallization. Interception at the aldehyde stage allowed for Z/E-isomerization, thus rendering the

  通过将使用O 2作为末端氧化剂的Cu催化的氧化与随后的亚氯酸盐氧化（Lindgren氧化）合并来实现烯丙基和苄醇氧化为相应的羧酸。对该方案进行了优化，以获得无需色谱或结晶的纯净产物。在醛阶段的拦截作用允许Z / E异构化，从而使氧化相对于起始原料的构型立体收敛。
• Stereoselective Synthesis of Isomers of the Naturally Occurring 13-Hydroxy-2,4,9-tetradecatrienoic Acid. Part II [1]
  作者：Christa Hoeller、Gottfried Reznicek、Antje Huefner

  DOI：10.1007/s00706-003-0097-y

  日期：2004.4.1

  The stereoselective syntheses of four unsaturated hydroxy fatty acids 13 S ,2 E ,4 E ,9 E )- 13-hydroxy-2,4,9-tetradecatrienoic acid, (13 S ,9 Z ,11 E )-13-hydroxy-9,11-tetradecadienoic acid, (13 S ,9 E , 11 E )-13-hydroxy-9,11-tetradecadienoic acid, and (13 S, 2 E, 4 E, 9 E )-13-hydroxy-2,4,9,11-tetradecatrienoic acid, are described. Wittig reactions, regioselective oxidation of dialcohol 3 , and

  四个不饱和羟基脂肪酸13 S ，2 E ，4 E ，9 E ）-13-羟基-2,4,9-十四碳三烯酸，（13 S ，9 Z ，11 E ）-13-羟基- 的立体选择性合成 9,11-十四碳二烯酸，（13 S ，9 E ，11 E ）-13-羟基-9,11-十四碳二烯酸和（13 S， 2 E， 4 E， 9 E ）-13- 羟基-2，描述了4,9,11-十四碳三烯酸。 维蒂希 反应，二醇的区域选择性氧化 3 和，使用非对映异构。
• Regioselective and Diastereoselective Allylic Amination Using Chlorosulfonyl Isocyanate. A Novel Asymmetric Synthesis of Unsaturated Aromatic 1,2-Amino Alcohols
  作者：Ji Duck Kim、Ok Pyo Zee、Young Hoon Jung

  DOI：10.1021/jo0267089

  日期：2003.5.1

  The diastereoselective synthesis of unsaturated aromatic 1,2-amino alcohols can be achieved on an epimeric mixture of optically active allylic ethers having a hydroxyl group attached to an allylic chiral center to the pi-system using chlorosulfonyl isocyanate. These reactions produced the unsaturated anti-1,2-amino alcohols either exclusively or predominantly only for aromatic derivatives. The anti-selectivity

  不饱和芳族1，2-氨基醇的非对映选择性合成可以使用氯磺酰基异氰酸酯在具有连接至π-系统的烯丙基手性中心的羟基的旋光性烯丙基醚的差向异构体混合物上实现。这些反应仅或主要仅对于芳族衍生物产生不饱和抗1,2-氨基醇。抗选择性可以由从醚到氨基甲酸酯的转化过程中的Cieplak电子模型来解释。
• One-Pot Oxidation/Isomerization of <i>Z</i>-Allylic Alcohols with Oxygen as Stoichiometric Oxidant
  作者：Daniel Könning、Wolf Hiller、Mathias Christmann

  DOI：10.1021/ol302420k

  日期：2012.10.19

  A method for generating (E)-alpha,beta-unsaturated aldehydes from Z-allylic alcohols or E/Z-mixtures is described. The one-pot procedure involves a Cu-catalyzed oxidation followed by an organocatalytic DE-isomerization with N,N-dimethylaminopyridine (DMAP).
• Stereoselective synthesis of allylic amines by rearrangement of allylic trifluoroacetimidates: stereoselective synthesis of polyoxamic acid and derivatives of other α-amino acids
  作者：Ian Savage、Eric J. Thomas、Peter D. Wilson

  DOI：10.1039/a905772b

  日期：——

  On heating in xylene under reflux, allylic trifluoroacetimidates undergo [3,3] sigmatropic rearrangement to regioisomeric allylic trifluoroacetamides. Examples include the rearrangements of the trifluoroacetimidates 16 and 73 to the trifluoroacetamides 17 and 74, which were incorporated into stereoselective syntheses of polyoxamic acid 1, and the rearrangement of the trifluoroacetimidate 26. The rearrangement was the key step in asymmetric syntheses of the (S)- and (R)-valine derivatives 37 and 48. Other examples include rearrangements of the trifluoroacetimidates 52, 54 and 56 prepared from geraniol, cinnamyl alcohol and sorbyl alcohol, respectively, and the more complex trifluoroacetimidates 62 and 69. The stereoselectivity of these rearrangements, which are somewhat faster than rearrangements of analogous allylic trichloroacetimidates, is consistent with the participation of chair-like, six-membered, transition structures.

  在甲苯中回流加热时，烯丙基三氟乙亚胺酸酯会发生[3,3] σ迁移重排，生成区域异构的烯丙基三氟乙酰胺。例如，三氟乙亚胺酸酯16和73重排生成三氟乙酰胺17和74，这些被用于合成聚氧基酸1的选择性合成中，以及三氟乙亚胺酸酯26的重排。这一重排是对映选择性合成(S)-和(R)-缬氨酸类似物37和48的关键步骤。其他例子包括由香叶醇、肉桂醇和苏儿醇分别制备的三氟乙亚胺酸酯52、54和56的重排，以及更复杂的三氟乙亚胺酸酯62和69的重排。这些重排的立体选择性比类似的烯丙基三氯乙亚胺酸酯重排稍快，与椅式六元过渡态结构的参与相符。