methyl (Z)-3-[(2S,3S)-3-[tert-butyl(dimethyl)silyl]oxiran-2-yl]prop-2-enoate | 328941-91-9

• 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 (Z)-3-[(2S,3S)-3-[tert-butyl(dimethyl)silyl]oxiran-2-yl]prop-2-enoate
• CAS: 328941-91-9
• 化学式: C₁₂H₂₂O₃Si
• 分子量: 242.39
• InChiKey: MRBFVEYMZBBFKL-PVRKFNRASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.53
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (Z)-3-[(2S,3S)-3-[tert-butyl(dimethyl)silyl]oxiran-2-yl]prop-2-enoate 在 亚磷酸三苯酯 、 palladium diacetate 作用下， 以 四氢呋喃 为溶剂， 以76%的产率得到(Z)-(S)-4-(tert-Butyl-dimethyl-silanyl)-5-oxo-pent-2-enoic acid methyl ester
  参考文献：
  名称：

  Stereocontrolled rearrangement of silylated vinyloxiranes into α-trialkylsilyl-β,γ-unsaturated aldehydes

  摘要：

  Silylated vinyloxiranes 1, substituted on the double bond, have been synthesized and reacted under very mild conditions in the presence of a catalytic amount of palladium (0). They rearrange into alpha-silylated-beta-gamma-unsaturated aldehydes 2, not only with complete chirality transfer but also with total retention of the double bond stereochemistry. (C) 1997 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01207-0
• 作为产物：
  描述：

  三甲基膦酰基乙酸酯 、 (2RS,3RS)-3-(tert-butyldimethylsilyl)-2,3-epoxypropanal 在 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 以10%的产率得到methyl (Z)-3-[(2S,3S)-3-[tert-butyl(dimethyl)silyl]oxiran-2-yl]prop-2-enoate
  参考文献：
  名称：

  Stereocontrolled rearrangement of silylated vinyloxiranes into α-trialkylsilyl-β,γ-unsaturated aldehydes

  摘要：

  Silylated vinyloxiranes 1, substituted on the double bond, have been synthesized and reacted under very mild conditions in the presence of a catalytic amount of palladium (0). They rearrange into alpha-silylated-beta-gamma-unsaturated aldehydes 2, not only with complete chirality transfer but also with total retention of the double bond stereochemistry. (C) 1997 Published by Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01207-0

文献信息

• Highly stereoselective generation of α-pyrones displaying four contiguous stereogenic centers
  作者：Frédéric Marion、Sandrine Calvet、Christine Courillon、Max Malacria

  DOI：10.1016/s0040-4039(02)00473-2

  日期：2002.4

  We report here an efficient one-pot diastereoselective procedure which transforms silylated vinyloxiranes 2 into enantiomerically pure tetrasubstituted δ-lactones 7, 10. This transformation includes four steps: palladium(0)-catalyzed rearrangement/alkylation-lactonization/1,4-conjugated addition/electrophilic trapping of the intermediary enolate. These reactions allow efficient control of four contiguous

  我们在这里报告其变换甲硅烷基化vinyloxiranes一种高效一锅非对映选择性方法2到对映体纯的四取代的δ内酯7，10。该转化包括四个步骤：中间烯醇化物的钯（0）催化的重排/烷基化-内酯化/ 1,4-共轭加成/亲电捕集。这些反应可以有效地控制四个连续的立体异构中心，当亲电试剂为前手性苯甲醛时，甚至可以控制第五个。
• One-Pot Diastereoselective Preparation of <i>α</i>,<i>β</i>-Unsaturated-<i>γ</i>-Silylated-<i>δ</i>-Lactones: Application towards Natural Compounds
  作者：Frédéric Marion、Rachel Le Fol、Christine Courillon、Max Malacria

  DOI：10.1055/s-2001-9700

  日期：——

  Rearrangement of silylated vinyloxiranes into highly functionalized α-silylated-β,γ-unsaturated aldehydes occurs with total chirality transfer and retention of double bond configuration under Pd(0) catalysis. We show that this reaction is a versatile tool in the field of total stereoselective synthesis: enantiomerically pure lactones are obtained. The pheromone 6-n-undecyltetrahydro-2-pyrone 2 and massoilactone, 5-hydroxy-2-decenoic acid lactone 3, are synthesized. We describe herein a novel highly diastereoselective route to α,β-unsaturated-γ-silylated-δ-substituted-δ-lactones 1.

  在Pd(0)催化下，硅化的乙烯氧杂环在重新排列过程中转化为高度功能化的α-硅化-β,γ-不饱和醛，同时实现了完全的手性转移及双键构型的保持。我们展示了这一反应作为全立体选择性合成领域的多功能工具：可以获得对映体纯的内酯。合成了信息素6-n-undecyltetrahydro-2-pyrone 2和质量内酯5-hydroxy-2-decenoic acid lactone 3。我们在此描述了一条新颖的高二面体选择性路线，以合成α,β-不饱和-γ-硅化-δ-取代的δ-内酯1。