(+/-)-(2R*,3R*,4R*,5R*)-4,5-Epoxy-3-methyl-1-<(tripropylsilyl)oxy>-2-hexanol

• 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: (+/-)-(2R*,3R*,4R*,5R*)-4,5-Epoxy-3-methyl-1-<(tripropylsilyl)oxy>-2-hexanol
• 英文别名: (+/-)-(2R,3R,4R,5R)-4,5-epoxy-3-methyl-1-[(triisopropylsilyl)oxy]-2-hexanol；(+/-)-(2R*,3R*,4R*,5R*)-4,5-Epoxy-3-methyl-1-[(tripropylsilyl)oxy]-2-hexanol；(2R,3R)-3-[(2R,3R)-3-methyloxiran-2-yl]-1-tri(propan-2-yl)silyloxybutan-2-ol
• 化学式: C₁₆H₃₄O₃Si
• 分子量: 302.53
• InChiKey: NDLHZVIMZQCGCM-LVQVYYBASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.96
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  42
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-(2R*,3R*,4R*,5R*)-4,5-Epoxy-3-methyl-1-<(tripropylsilyl)oxy>-2-hexanol 在 sodium hydroxide 、 正丁基锂 、 氯化二乙基铝 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 22.0h， 生成
  参考文献：
  名称：

  用取代的炔铝试剂区域选择性裂解 3,4-环氧醇：在聚丙酸酯的立体选择性合成中的应用。

  摘要：

  3-O-取代的丙炔基铝试剂与 TIPS 保护的 2,3-环氧醇和几种非对映异构 2-甲基-3,4-环氧醇的反应为烯丙醇的后续制备和环氧化提供了一种方便的合成方法。产率低至中等，区域选择性（内部与外部攻击）与标准二乙基丙炔基铝试剂相似。TMS-乙炔丙烷试剂提高了产率和良好的区域选择性，是受阻环氧化物裂解的首选试剂。这种有吸引力的方法被应用于两个先进的聚丙酸酯前体片段的制作。

  DOI：

  10.1016/j.tet.2007.05.122
• 作为产物：
  描述：

  (+/-)-trans-syn-3-Methyl-1-<(triisopropylsilyl)oxy>-4-hexen-2-ol 在 叔丁基过氧化氢 、 hexacarbonyl molybdenum 作用下， 以 甲苯 为溶剂， 反应 3.0h， 生成 (+/-)-(2R*,3R*,4S*,5S*)-4,5-Epoxy-3-methyl-1-<(triisopropylsilyl)oxy>-2-hexanol 、 (+/-)-(2R*,3R*,4R*,5R*)-4,5-Epoxy-3-methyl-1-<(tripropylsilyl)oxy>-2-hexanol
  参考文献：
  名称：

  Microwave-assisted epoxidation of hindered homoallylic alcohols using VO(acac)2: application to polypropionate synthesis

  摘要：

  The VO(acac)(2) catalyzed epoxidation of hindered homoallylic alcohols was conducted under microwave irradiation in an open vessel using toluene as solvent. The reaction time for the epoxidation of a series of cis- and trans-2-methyl-3-alkenols was dramatically reduced from 6 to 10 days to less than 3 h when compared to conventional heating. The cis alkenols exhibited very high diastereoselectivity. The more elaborated polypropionate precursors 12, 14 and 16 were epoxidized in good yield and excellent diastereoselectivities using the microwave-assisted epoxidation technique described here, which is safe and suitable for multi-gram scales. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.08.095

文献信息

• Concise epoxide-based synthesis of the C14–C25 bafilomycin A1 polypropionate chain
  作者：Elizabeth M. Valentín、Marlenne Mulero、José A. Prieto

  DOI：10.1016/j.tetlet.2012.02.067

  日期：2012.4

  An efficient nonaldol convergent synthesis of the C14–C25 polyketide fragment of bafilomycin A1 was completed in 16% overall yield and 8 steps in its longest linear sequence. This synthesis highlights the formation of the key fragments using a three-step sequence of epoxide cleavage, alkyne reduction, and epoxidation developed in our laboratory; starting from suitably protected enantiomeric epoxides

  bafilomycin A 1的 C14-C25 聚酮化合物片段的高效壬醛聚合合成以 16% 的总产率和最长线性序列的 8 个步骤完成。该合成使用我们实验室开发的环氧化物裂解、炔烃还原和环氧化的三步序列突出了关键片段的形成；从适当保护的反式-2,3-环氧丁醇的对映体环氧化物开始。这种化学反应代表了巴弗洛霉素 A 1聚酮链的快速不对称和非对映选择性构建，其中每个立体中心都是仅使用环氧化物化学构建的。
• Highly Regioselective Copper-Catalyzed <i>cis</i>- and <i>trans</i>-1-Propenyl Grignard Cleavage of Hindered Epoxides. Application in Propionate Synthesis
  作者：David Rodríguez、Marlenne Mulero、José A. Prieto

  DOI：10.1021/jo060833t

  日期：2006.7.1

  Hindered protected and unprotected epoxy alcohols were regioselectively cleaved using copper-catalyzed cis- and trans-1-propenylmagnesium bromide. The reaction exhibited good yield and excellent regioselectivity in systems where organocuprates and organoalanes failed. The cis Grignard reagent displayed no double-bond isomerization, whereas the trans isomer showed partial trans-to-cis equilibration

  使用铜催化的顺式和反式-1-丙烯基溴化镁区域选择性地裂解受阻的受保护和未保护的环氧醇。在有机铜酸盐和有机丙氨酸失效的体系中，该反应显示出良好的产率和优异的区域选择性。所述顺式格利雅试剂显示没有双键异构化，而反式异构体显示出部分的反式-到-顺平衡，这是通过控制试剂形成条件最小化。该反应显示出对C10-C15链霉菌素D ansa链片段的修饰非常有用。
• Stereochemistry of the iodocarbonatation of cis- and trans-3-methyl-4-pentene-1,2-diols: the unusual formation of several anti iodo carbonates
  作者：Raymond Tirado、Jose A. Prieto

  DOI：10.1021/jo00073a027

  日期：1993.10

  A study on the stereoselective preparation of a series of 3-methyl-4,5-epoxy alcohols as an entry to polypropionates was undertaken. Initially, the opening of cis and trans TIPS-protected 2,3-epoxy butanols by propynyldiethylalane showed an excellent regioselectivity favoring the monoprotected 1,2-diol products. The resulting propargylic alcohols were stereoselectively reduced to the cis and trans 1-[(triisopropylsilyl)oxy]-3-methyl-4-hexen-2-ols. Iodocarbonatation of these four isomeric homoallylic alcohols was carried out and the stereochemistry of the intermediate iodo carbonates established. Interestingly, a complete anti selectivity (>20:1 anti:syn) was observed when both the syn 3-methyl and cis double-bond geometry were present (3b, 10, and 20). The anti relative configuration for all of the iodo carbonates was established by NMR, and that of 5b was confirmed by X-ray crystallography. This study demonstrated that the relative stereochemistry of the hydroxyl and C(3) methyl groups in combination with the cis or trans geometry of the alkene exerts a significant effect on the stereochemical outcome of the iodocarbonatation reaction. Methanolysis of the iodo carbonates produced the desired 3-methyl-4,5-epoxy alcohols. The application of this chemistry to the reiterative synthesis of polypropionates was carried out with epoxy alcohol 4a (anti isomer), producing a new homologated epoxy alcohol, 22, with six contiguous stereocenters in a highly stereoselective manner.
• Regioselective cleavage of cis- and trans-2-methyl-3,4-epoxy alcohols with diethylpropynyl aluminum
  作者：Raymond Tirado、Gerardo Torres、Wildeliz Torres、José A. Prieto

  DOI：10.1016/j.tetlet.2004.12.018

  日期：2005.1

  The regioselectivity of the reaction of diethylpropynyl aluminum with diastereomeric 2-methyl-3-4-epoxy alcohols was studied. The preferred side of attack (1,3-diol vs 1,4-diol product) depends on the stereochemical disposition of the substituents. NMR studies showed that the regiochemistry of this reaction is governed by the aluminum coordination pattern. Protection of the alcohol with MEM provides the 1,3-diol product in systems where the free alcohol produced the 1,4-diols. (C) 2004 Elsevier Ltd. All rights reserved.