(2E)-2-methyl-3-(2-methyl(1,3-oxazol-4-yl))-1-triisopropylsilyloxyprop-2-ene | 234075-91-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: (2E)-2-methyl-3-(2-methyl(1,3-oxazol-4-yl))-1-triisopropylsilyloxyprop-2-ene
• 英文别名: [(E)-2-methyl-3-(2-methyl-1,3-oxazol-4-yl)prop-2-enoxy]-tri(propan-2-yl)silane
• CAS: 234075-91-3
• 化学式: C₁₇H₃₁NO₂Si
• 分子量: 309.524
• InChiKey: AZMPZQXNMNYGHR-OQLLNIDSSA-N

物化性质

• 沸点：
  360.472±30.00 °C(Press: 760.00 Torr)(predicted)
• 密度：
  0.936±0.06 g/cm3(Temp: 25 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.58
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  35.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2E)-2-methyl-3-(2-methyl(1,3-oxazol-4-yl))-1-triisopropylsilyloxyprop-2-ene 在 lithium diethylamide 作用下， 以 四氢呋喃 、 氘代四氢呋喃 、 正己烷 为溶剂， 生成 (2E)-2-methyl-3-[2-(lithiomethyl)(1,3-oxazol-4-yl)]-1-triisopropylsilyloxyprop-2-ene 、 (2E)-2-methyl-3-(5-lithio-2-methyl(1,3-oxazol-4-yl))-1-triisopropylsilyloxyprop-2-ene
  参考文献：
  名称：

  Selective Lithiation of 2-Methyloxazoles. Applications to Pivotal Bond Constructions in the Phorboxazole Nucleus

  摘要：

  The lithiation of 2-methyloxazoles with alkyllithium and hindered lithium amide bases generally results in the competitive formation of a mixture of 5-lithio- and 2-(lithiomethyl)oxazole isomers. Herein a synthetically useful lithiation method which allows for the selective formation of 2-(lithiomethyl)oxazole is described. Diethylamine has been found to be a kinetically competent proton source that will mediate the equilibration of the kinetically formed 5-lithiooxazole to its more stable 2-(lithiomethyl)oxazole counterpart. Application of this metalation strategy with lithium diethylamide to two important bond constructions relevant to a projected phorboxazole synthesis is presented.

  DOI：

  10.1021/ol990027r
• 作为产物：
  描述：

  三异丙基硅基三氟甲磺酸酯 、 2-methyl-3-[4-methyl(3,5-oxazolyl)]prop-2-en-1-ol 在 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.25h， 以91%的产率得到(2E)-2-methyl-3-(2-methyl(1,3-oxazol-4-yl))-1-triisopropylsilyloxyprop-2-ene
  参考文献：
  名称：

  Selective Lithiation of 2-Methyloxazoles. Applications to Pivotal Bond Constructions in the Phorboxazole Nucleus

  摘要：

  The lithiation of 2-methyloxazoles with alkyllithium and hindered lithium amide bases generally results in the competitive formation of a mixture of 5-lithio- and 2-(lithiomethyl)oxazole isomers. Herein a synthetically useful lithiation method which allows for the selective formation of 2-(lithiomethyl)oxazole is described. Diethylamine has been found to be a kinetically competent proton source that will mediate the equilibration of the kinetically formed 5-lithiooxazole to its more stable 2-(lithiomethyl)oxazole counterpart. Application of this metalation strategy with lithium diethylamide to two important bond constructions relevant to a projected phorboxazole synthesis is presented.

  DOI：

  10.1021/ol990027r

文献信息

• Application of Complex Aldol Reactions to the Total Synthesis of Phorboxazole B
  作者：David A. Evans、Duke M. Fitch、Thomas E. Smith、Victor J. Cee

  DOI：10.1021/ja002356g

  日期：2000.10.1

  The synthesis of phorboxazole B has been accomplished in 27 linear steps and an overall yield of 12.6%. The absolute stereochemistry of the C4−C12, C33−C38, and C13−C19 fragments was established utilizing catalytic asymmetric aldol methodology, while the absolute stereochemistry of the C20−C32 fragment was derived from an auxiliary-based asymmetric aldol reaction. All remaining chirality was incorporated

  佛盒唑B的合成分27个线性步骤完成，总收率为12.6%。C4-C12、C33-C38 和 C13-C19 片段的绝对立体化学是利用催化不对称醛醇方法建立的，而 C20-C32 片段的绝对立体化学来自基于辅助的不对称醛醇反应。所有剩余的手性都是通过内部不对称诱导引入的，除了来自 (R)-三苯甲基缩水甘油的 C43 立体中心。关键片段偶联包括立体选择性双立体分化醛醇反应、金属化恶唑烷基化、恶唑稳定的 Wittig 烯化和完全精心设计的烯基金属侧链的螯合控制添加。
• Asymmetric Synthesis of Phorboxazole B—Part I: Synthesis of the C20-C38 and C39-C46 Subunits
  作者：David A. Evans、Victor J. Cee、Thomas E. Smith、Duke M. Fitch、Patricia S. Cho

  DOI：10.1002/1521-3773(20000717)39:14<2533::aid-anie2533>3.0.co;2-b

  日期：2000.7.17