(+/-)-trans-syn-3-Methyl-1-<(triisopropylsilyl)oxy>-4-hexen-2-ol

• 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: (+/-)-trans-syn-3-Methyl-1-<(triisopropylsilyl)oxy>-4-hexen-2-ol
• 英文别名: (E,2R,3S)-3-methyl-1-tri(propan-2-yl)silyloxyhex-4-en-2-ol
• 化学式: C₁₆H₃₄O₂Si
• 分子量: 286.53
• InChiKey: ZNGXTJPADGWDKD-IGXNXKSNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-trans-syn-3-Methyl-1-<(triisopropylsilyl)oxy>-4-hexen-2-ol 在 bis(acetylacetonate)oxovanadium 作用下， 以 氘代甲苯 、 甲苯 为溶剂， 反应 3.08h， 生成
  参考文献：
  名称：

  来自高度取代的3,4-环氧醇的烷氧基铝配合物：NMR和计算研究

  摘要：

  有机铝介导的环氧醇的环氧开环是基于环氧乙烷的聚丙烯酸酯合成方法中的关键步骤。然而，当应用于2-甲基-3,4-环氧醇时，该反应显示出意外的区域选择性。为了深入了解控制环氧化物开环过程的因素，非对映异构的2-甲基-3,4-环氧醇与三乙基铝反应，以鉴定由这些系统形成的铝络合物。使用头算HF / [13s7p / 11s5p]和B3PW91 / 6-31G **量规（包括原子轨道（GIAO）方法）计算了不同的环氧化物-铝络合物，并将其与实验NMR数据进行了比较。计算和实验数据与铝二聚物配合物（TIPSOCH 2 CH（OAlEt 2）CH（CH）3 CHCH（O）（AlEt 3））2（VIII）用于有利于外部C4环氧碳的亲核攻击的体系，而不常见的三聚种TIPSOCH 2 CH（OAlEt 2）CH（CH）3 CHCH（O）（AlEt 3）2（X）与支持内部C3攻击的系统一致。在27个的Al NMR

  DOI：

  10.1002/poc.3024
• 作为产物：
  描述：

  (E)-(but-2-en-1-yloxy)triisopropylsilane 在 正丁基锂 、 氨 、 sodium 、 氯化二乙基铝 作用下， 以 四氢呋喃 、 乙醇 、 叔丁醇 为溶剂， 反应 70.0h， 生成 (+/-)-trans-syn-3-Methyl-1-<(triisopropylsilyl)oxy>-4-hexen-2-ol
  参考文献：
  名称：

  Stereochemistry of the iodocarbonatation of cis- and trans-3-methyl-4-pentene-1,2-diols: the unusual formation of several anti iodo carbonates

  摘要：

  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.

  DOI：

  10.1021/jo00073a027

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。
• Microwave-assisted epoxidation of hindered homoallylic alcohols using VO(acac)2: application to polypropionate synthesis
  作者：Gerardo Torres、Wildeliz Torres、José A. Prieto

  DOI：10.1016/j.tet.2004.08.095

  日期：2004.11

  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.
• 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.
• Aluminum alkoxide complexes from highly substituted 3,4-epoxy alcohols: An NMR and computational study
  作者：Gerardo Torres、Yasuyuki Ishikawa、José A. Prieto

  DOI：10.1002/poc.3024

  日期：2012.12

  organoaluminum mediated epoxide ring opening of epoxy alcohols is a key step in the oxirane‐based approach for polypropionate synthesis. However, this reaction has shown unanticipated regioselectivities when applied to 2‐methyl‐3,4‐epoxy alcohols. In order to gain mechanistic insight into the factors controlling the epoxide ring opening process, diastereomeric 2‐methyl‐3,4‐epoxy alcohols were reacted with triethylaluminum

  有机铝介导的环氧醇的环氧开环是基于环氧乙烷的聚丙烯酸酯合成方法中的关键步骤。然而，当应用于2-甲基-3,4-环氧醇时，该反应显示出意外的区域选择性。为了深入了解控制环氧化物开环过程的因素，非对映异构的2-甲基-3,4-环氧醇与三乙基铝反应，以鉴定由这些系统形成的铝络合物。使用头算HF / [13s7p / 11s5p]和B3PW91 / 6-31G **量规（包括原子轨道（GIAO）方法）计算了不同的环氧化物-铝络合物，并将其与实验NMR数据进行了比较。计算和实验数据与铝二聚物配合物（TIPSOCH 2 CH（OAlEt 2）CH（CH）3 CHCH（O）（AlEt 3））2（VIII）用于有利于外部C4环氧碳的亲核攻击的体系，而不常见的三聚种TIPSOCH 2 CH（OAlEt 2）CH（CH）3 CHCH（O）（AlEt 3）2（X）与支持内部C3攻击的系统一致。在27个的Al NMR