(+/-)-(2R,3R,4R,5S)-3,5-dimethyl-1-[(triisopropylsilyl)oxy]-6-octyn-2,4-diol

• 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,5S)-3,5-dimethyl-1-[(triisopropylsilyl)oxy]-6-octyn-2,4-diol
• 英文别名: (2R,3R,4R,5R)-3,5-dimethyl-1-tri(propan-2-yl)silyloxyoct-6-yne-2,4-diol
• 化学式: C₁₉H₃₈O₃Si
• 分子量: 342.594
• InChiKey: RZYSLCOQBCKOMG-YDZRNGNQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+/-)-(2R,3R,4R,5S)-3,5-dimethyl-1-[(triisopropylsilyl)oxy]-6-octyn-2,4-diol 在 palladium on activated charcoal 喹啉 、 叔丁基过氧化氢 、 bis(acetylacetonate)oxovanadium 、 氢气 、 4-甲基苯磺酸吡啶 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 0.17h， 生成 (+/-)-(4S,5S,6S)-4-[(1S,2S,3S)-1,3-dimethyl-2-hydroxy-4-hexynyl]-6-[(triisopropylsilyloxy)methyl]-2,2,5-trimethyl-1,3-dioxane
  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
• 作为产物：
  描述：

  (+/-)-(2S,3R,4Z)-3-methyl-1-[(triisopeopylsilyl)oxy]-4-hexen-2-ol 在 叔丁基过氧化氢 、 bis(acetylacetonate)oxovanadium 作用下， 以 甲苯 为溶剂， 反应 0.75h， 生成 (+/-)-(2R,3R,4R,5S)-3,5-dimethyl-1-[(triisopropylsilyl)oxy]-6-octyn-2,4-diol
  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

• Regioselective cleavage of 3,4-epoxy alcohols with substituted alkynylaluminum reagents: application to the stereoselective synthesis of polypropionates
  作者：Wilnelia Dávila、Wildeliz Torres、José A. Prieto

  DOI：10.1016/j.tet.2007.05.122

  日期：2007.8

  reaction of 3-O-substituted propynyl aluminum reagents with a TIPS-protected 2,3-epoxy alcohol and several diastereomeric 2-methyl-3,4-epoxy alcohols offers a convenient synthetic approach for the subsequent preparation and epoxidation of allylic alcohols. The yields are low to moderate and the regioselectivity (internal vs external attack) similar to that of the standard diethylpropynyl aluminum reagent

  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。
• Stereoselective Construction of all-<i>anti</i> Polypropionate Modules: Synthesis of the C5−C10 Fragment of Streptovaricin U
  作者：Wildeliz Torres、Raúl R. Rodríguez、José A. Prieto

  DOI：10.1021/jo8026966

  日期：2009.3.20

  A concise nonaldol approach for the stereoselective construction of all-anti polypropionate fragments was developed. The iterative epoxide-based methodology consists of the syn-selective epoxidation of cis homoallylic alcohols with use of the VO(acac)2-catalyzed conditions followed by epoxide cleavage with a propynyl aluminum reagent as key steps. The methodology was applied to the synthesis of the

  开发了一种用于立体选择性构建全抗聚丙酸酯片段的简洁的壬醛醇方法。基于迭代环氧化物的方法包括使用 VO(acac) 2催化条件对顺式高烯丙醇进行顺式选择性环氧化，然后用丙炔基铝试剂进行环氧化物裂解作为关键步骤。该方法用于合成链球菌 U的全抗C6-C10 片段。
• 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.
• 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.