methyl (+/-)-5-(tert-butyldimethylsilyl)oxyhexanoate | 172172-33-7

• 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 (+/-)-5-(tert-butyldimethylsilyl)oxyhexanoate
• 英文别名: methyl 5-((tert-butyldimethylsilyl)oxy)hexanoate；Methyl 5-[tert-butyl(dimethyl)silyl]oxyhexanoate
• CAS: 172172-33-7
• 化学式: C₁₃H₂₈O₃Si
• 分子量: 260.449
• InChiKey: FHJFAPXMOOQKQI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.74
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (+/-)-5-(tert-butyldimethylsilyl)oxyhexanoate 在 盐酸 、 甲醇 、 二氯甲烷 、 双(三甲基硅烷基)氨基钾 、 2-(Phenylsulfonyl)-3-phenyloxaziridin 作用下， 反应 2.5h， 生成 (2S,5R)-2-hydroxy-5-methyl-δ-valerolactone
  参考文献：
  名称：

  Enantiospecific Synthesis of (+)- and (−)-Ferruginine from l-Glutamic Acid. Synthesis of Tropanes via Intramolecular Iminium Ion Cyclization

  摘要：

  Iminium ions, generated by decarbonylation of N-benzyl-5-[1-(methoxycarbonyl)-4-oxopentyl]-prolines, prolines, undergo intramolecular cyclization to afford 2,4-disubstituted tropanes in good yields. This transformation is also shown to be a stereospecific reaction. The value of these substituted tropanes has been demonstrated by functional group manipulation, leading to the enantiospecific synthesis of (+)-ferruginine, an alkaloid isolated from Darlinga ferruginea, and its unnatural enantiomer, (-)-ferruginine.

  DOI：

  10.1021/jo9515081
• 作为产物：
  描述：

  丁位己内酯 在 咪唑 、 sodium 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 methyl (+/-)-5-(tert-butyldimethylsilyl)oxyhexanoate
  参考文献：
  名称：

  通过束缚闭环复分解立体选择性合成2Z，4E-构的烯酸酯

  摘要：

  摘要 描述了从外消旋烯丙醇和乙烯基乙酸到（2 Z，4 E）二烯酸乙酯的两步序列。该序列涉及反应物的Steglich酯化，然后是一锅闭环易位-碱基诱导的消除-烷基化反应，以高立体选择性提供产物。使用Meerwein盐Et 3 OBF 4可以有效地完成中间体羧酸钠的捕集。 描述了从外消旋烯丙醇和乙烯基乙酸到（2 Z，4 E）二烯酸乙酯的两步序列。该序列涉及反应物的Steglich酯化，然后是一锅闭环易位-碱基诱导的消除-烷基化反应，以高立体选择性提供产物。使用Meerwein盐Et 3 OBF 4可以有效地完成中间体羧酸钠的捕集。

  DOI：

  10.1055/s-0035-1562536

文献信息

• Synthesis of Two Subunits of the Macrolide Domain of the Immunosuppressive Agent Sanglifehrin A and Assembly of a Macrolactone Precursor. Application of Masamune <i>anti</i>-Aldol Condensation
  作者：Khomson Suttisintong、James D. White

  DOI：10.1021/jo5027595

  日期：2015.2.20

  Asymmetric anti-aldol coupling of a norephedrine-derived ester with an a-chiral aldehyde was used to synthesize a carboxylic acid representing the C13-C19 segment of the macrocyclic domain present in the immunosuppressive agent sanglifehrin A. Felkin addition set configuration at the C14-C17 stereotetrad in this unit in which hydroxyl functions at C15 and C17 were masked as an internal ketal. The carboxyl group of this segment was coupled to the N-terminus of the tripeptide portion (C1-N12) of sanglifehrin A macrolactone to assemble the C1-C19 domain. Synthesis of the C20-C25 subunit of sanglifehrin A containing a (23S) alcohol was completed via asymmetric allylation of (E)-3-iodo-2-methylprop-2-enal followed by oxidative cleavage of the terminal vinyl appendage and a Takai olefination with pinacol dichloromethylboronate. Esterification of this alcohol with a C1-C19 carboxylic acid furnished an open C1-C25 macrolactone precursor, but this substance failed to undergo macrocyclization via intramolecular SuzukiMiyaura coupling.
• Enantiospecific Synthesis of (+)- and (−)-Ferruginine from <scp>l</scp>-Glutamic Acid. Synthesis of Tropanes <i>via</i> Intramolecular Iminium Ion Cyclization
  作者：Andrés S. Hernández、Adrian Thaler、Josep Castells、Henry Rapoport

  DOI：10.1021/jo9515081

  日期：1996.1.1

  Iminium ions, generated by decarbonylation of N-benzyl-5-[1-(methoxycarbonyl)-4-oxopentyl]-prolines, prolines, undergo intramolecular cyclization to afford 2,4-disubstituted tropanes in good yields. This transformation is also shown to be a stereospecific reaction. The value of these substituted tropanes has been demonstrated by functional group manipulation, leading to the enantiospecific synthesis of (+)-ferruginine, an alkaloid isolated from Darlinga ferruginea, and its unnatural enantiomer, (-)-ferruginine.
• Stereoselective Synthesis of 2Z,4E-Configured Dienoates through Tethered Ring Closing Metathesis
  作者：Bernd Schmidt、Stephan Audörsch、Oliver Kunz

  DOI：10.1055/s-0035-1562536

  日期：——

  is described. The sequence involves Steglich esterification of the reactants, followed by a one-pot ring closing metathesis–base induced elimination–alkylation reaction to furnish the products in high stereoselectivity. Trapping of the intermediate sodium carboxylates is accomplished efficiently using Meerwein’s salt Et3OBF4. A two-step sequence leading from racemic allylic alcohols and vinylacetic

  摘要 描述了从外消旋烯丙醇和乙烯基乙酸到（2 Z，4 E）二烯酸乙酯的两步序列。该序列涉及反应物的Steglich酯化，然后是一锅闭环易位-碱基诱导的消除-烷基化反应，以高立体选择性提供产物。使用Meerwein盐Et 3 OBF 4可以有效地完成中间体羧酸钠的捕集。 描述了从外消旋烯丙醇和乙烯基乙酸到（2 Z，4 E）二烯酸乙酯的两步序列。该序列涉及反应物的Steglich酯化，然后是一锅闭环易位-碱基诱导的消除-烷基化反应，以高立体选择性提供产物。使用Meerwein盐Et 3 OBF 4可以有效地完成中间体羧酸钠的捕集。