Methyl 4-hydroxy-1-(trimethylsilyl)-5-hexynoate | 118800-11-6

• 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: Methyl 4-hydroxy-1-(trimethylsilyl)-5-hexynoate
• 英文别名: (S)-methyl 4-hydroxy-6-(trimethylsilyl)hex-5-ynoate；methyl (4S)-4-hydroxy-6-trimethylsilylhex-5-ynoate
• CAS: 118800-11-6
• 化学式: C₁₀H₁₈O₃Si
• 分子量: 214.337
• InChiKey: VMVWFJDZNOOKIW-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.18
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Methyl 4-hydroxy-1-(trimethylsilyl)-5-hexynoate 在 咪唑 、 18-冠醚-6 、 potassium fluoride dihydrate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 (4S)-methyl 4-(t-butyldimethylsilyloxy)-hex-5-ynoate
  参考文献：
  名称：

  First total synthesis of the anti-inflammatory lipid mediator Resolvin D6

  摘要：

  The first total synthesis of Resolvin D6, an endogenous lipid mediator of resolution of inflammation derived from docosahexaenoic acid, has been achieved. The chiral hydroxy-groups at C4 and C17 were generated via an asymmetric Noyori transfer hydrogenation and a Sharpless catalytic asymmetric epoxidation, respectively. A mild copper catalyzed coupling of cis-1,4-dibromo-2-butene with TMS-acetylene generated the C7-C14 fragment. Pd-0/Cu-I Sonogashira couplings and Zn(Cu/Ag) reduction completed the synthesis of Resolvin D6. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.11.003
• 作为产物：
  描述：

  methyl 4-oxo-6-(trimethylsilyl)hex-5-ynoate 在 Noyori's catalyst 作用下， 以 异丙醇 为溶剂， 反应 15.0h， 以93%的产率得到Methyl 4-hydroxy-1-(trimethylsilyl)-5-hexynoate
  参考文献：
  名称：

  硫代碘化物A C13–C29片段的合成：碘内酯化的立体化学过程中的烯丙基不对称诱导

  摘要：

  描述了莱奥多利德A C13–C29片段的立体控制合成。该天然产物是从深海海洋海绵皮癣菌中分离出来的。高度选择性的斯蒂勒交叉偶联用于组装带有C15烯丙基醇的（Z，E）-二烯，然后进行碘内酯化，引入C16-C17邻位立体中心。还讨论了基于烯丙基不对称诱导产生的固体机制基础的碘伏内酯化的立体化学过程。

  DOI：

  10.1016/j.tetlet.2015.10.087

文献信息

• Asymmetric reductions of propargyl ketones
  作者：M. Mark midland、Alfonso tramontano、Aleksander kazubski、Richard S. graham、David J.S. tsai、Daniel B. cardin

  DOI：10.1016/s0040-4020(01)82422-4

  日期：1984.1

  Propargyl ketones are readily reduced by the asymmetric reducing agent B-3-pinanyl-9- borabicyclo[3.3.1]-nonane (Alpine-borane). The reagent prepared from (+)-α-pinene and 9-BBN provides the R enantiomer while the S enantiomer can be obtained from (-)-α-pinene. Alternatively the S enantiomer can be prepared from the reagent derived from 9-BBN and the benzyl ether of nopol (6,6-dimethyl-bicyclo[3.11

  炔丙基酮很容易被不对称还原剂B -3-pinanyl-9- borabicyclo [3.3.1]-壬烷（Alpine-borane）还原。由（+）-α-pine烯和9-BBN制备的试剂可提供R对映体，而S对映异构体可获自（-）-α-obtained烯。或者，S对映异构体可以由衍生自9-BBN和nopol的苄基醚（6，6-二甲基-双环[3.11。]庚-2-烯-2-乙醇）的试剂制备。获得高对映体诱导的限制因素通常是α--烯的对映体纯度。用100％对映体纯的α-pine烯，可获得基本上100％ee的炔丙醇。提出了导致这种显着选择的过渡态的预测合理化。炔丙醇的乙炔单元为转化为其他有用的旋光产物提供了方便的方法。说明了炔丙醇在合成光学活性的α-和β-取代的γ-内酯以及δ-内酯中的用途。
• Lactobacillus kefir alcohol dehydrogenase: a useful catalyst for synthesis
  作者：Curt W. Bradshaw、Werner Hummel、Chi Huey Wong

  DOI：10.1021/jo00031a037

  日期：1992.2

  The alcohol dehydrogenase from Lactobacillus kefir simultaneously catalyzes carbonyl reductions and NADPH regeneration in the presence of 2-propanol. Representative synthesis of a number of chiral alcohols was accomplished in good yield and high enantiomeric excess (94-99%). This NADPH-requiring enzyme transfers the pro-R hydride from the cofactor to the si face of carbonyls to give (R) alcohols. The enzyme exhibits a very broad substrate specificity and high enantioselectivity for the synthesis of chiral aromatic, cyclic, polycyclic, and aliphatic alcohols.
• Synthesis of the C13–C29 fragment of leiodolide A: allylic asymmetric induction on the stereochemical course of iodolactonization
  作者：Jihoon Lee、James S. Panek

  DOI：10.1016/j.tetlet.2015.10.087

  日期：2015.12

  selective Stille cross-coupling was employed to assemble the (Z,E)-diene bearing the C15 allylic alcohol, which was followed by iodolactonization to introduce C16–C17 vicinal stereocenters. The stereochemical course of iodolactonization that is based on the solid mechanistic underpinnings arising from allylic asymmetric induction is also discussed.

  描述了莱奥多利德A C13–C29片段的立体控制合成。该天然产物是从深海海洋海绵皮癣菌中分离出来的。高度选择性的斯蒂勒交叉偶联用于组装带有C15烯丙基醇的（Z，E）-二烯，然后进行碘内酯化，引入C16-C17邻位立体中心。还讨论了基于烯丙基不对称诱导产生的固体机制基础的碘伏内酯化的立体化学过程。
• First total synthesis of the anti-inflammatory lipid mediator Resolvin D6
  作者：Ana R. Rodriguez、Bernd W. Spur

  DOI：10.1016/j.tetlet.2011.11.003

  日期：2012.1

  The first total synthesis of Resolvin D6, an endogenous lipid mediator of resolution of inflammation derived from docosahexaenoic acid, has been achieved. The chiral hydroxy-groups at C4 and C17 were generated via an asymmetric Noyori transfer hydrogenation and a Sharpless catalytic asymmetric epoxidation, respectively. A mild copper catalyzed coupling of cis-1,4-dibromo-2-butene with TMS-acetylene generated the C7-C14 fragment. Pd-0/Cu-I Sonogashira couplings and Zn(Cu/Ag) reduction completed the synthesis of Resolvin D6. (C) 2011 Elsevier Ltd. All rights reserved.