(E)-(2S,3S)-Methyl 2-methoxy-3-(dimethylphenylsilyl)hex-4-enoate | 134333-46-3

• 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: (E)-(2S,3S)-Methyl 2-methoxy-3-(dimethylphenylsilyl)hex-4-enoate
• 英文别名: (E)-(2S,3S)-methyl 3-(dimethylphenylsilyl)-2-methoxyhex-4-enoate；(2S,3S,4E)-Methyl 2-methoxy-3-(dimethylphenylsilyl)hexenoate；methyl (E,2S,3S)-3-[dimethyl(phenyl)silyl]-2-methoxyhex-4-enoate
• CAS: 134333-46-3
• 化学式: C₁₆H₂₄O₃Si
• 分子量: 292.45
• InChiKey: QRWOBOBPYKWSCU-SZVFQDTKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.74
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-甲基丙烯醛 、 (E)-(2S,3S)-Methyl 2-methoxy-3-(dimethylphenylsilyl)hex-4-enoate 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以73%的产率得到methyl (2R)-2-[(1S,2R,4S,5R)-5-[dimethyl(phenyl)silyl]-2-formyl-2,4-dimethylcyclopentyl]-2-methoxyacetate
  参考文献：
  名称：

  Conjugate addition reactions of chiral (E)-crotylsilanes: application to an asymmetric [3 + 2] cyclopentane annulation

  摘要：

  Functionalized (E)-crotylsilanes 1 undergo Lewis acid promoted conjugate addition reactions with alpha-substituted enals and methyl vinyl ketone 2 to produce tetrasubstituted cyclopentanes 3 with high levels of diastereoselection. The reaction is believed to proceed by an initial 1,4-addition which is followed by a 1,2-silyl migration and a final cyclization step involving the derived boron enolate resulting in the construction of the cyclopentanoid product.

  DOI：

  10.1021/jo00061a001

文献信息

• Asymmetric Synthesis of Homoallylic Amines and Functionalized Pyrrolidines via Direct Amino-Crotylation of In Situ Generated Imines
  作者：Jennifer V Schaus、Nareshkumar Jain、James S Panek

  DOI：10.1016/s0040-4020(00)00870-x

  日期：2000.12

  The asymmetric synthesis of functionalized homoallylic amines and silyl functionalized pyrrolidines through the Lewis acid promoted condensation of chiral (E)-crotylsilanes with sulfonyl imines and in situ generated N-acyl imines is described. We had anticipated that this bond construction could be used in the asymmetric synthesis of the N-terminal amino acid subunit of the nikkomycins. Aryl sulfonyl

  描述了通过路易斯酸促进手性（E）-巴豆基硅烷与磺酰基亚胺和原位产生的N-酰基亚胺的缩合的官能化均烯丙基胺和甲硅烷基官能化吡咯烷的不对称合成。我们已经预料到，该键结构可用于尼克霉素的N-末端氨基酸亚基的不对称合成。芳基磺酰亚胺缩合与手性在存在BF的硅烷试剂3 ·OET 2以形成具有可用水平的高烯丙基芳基磺酰基胺合成的选择性。对于涉及芳基N的情况-酰基亚胺我们已经知道温度控制反应的过程。例如，在-78°C或更低的温度下，主要产物是吡咯烷，而在更高的温度（-30至-20°C）下，生成均烯丙基胺。对于所研究的情况，[3 + 2]环限于芳基亚胺衍生物，因为烷基和支链亚胺无法生成吡咯烷衍生物：较高的反应温度促进了环化产物向均烯丙基胺的转化。在与原位生成的亚胺的双立体分化反应中，形成带有syn - anti和syn - syn立体化学三元组的仲胺可实现良好的选择性。
• Panek, James S.; Yang, Michael, Journal of the American Chemical Society, 1991, vol. 113, # 17, p. 6594 - 6600
  作者：Panek, James S.、Yang, Michael

  DOI：——

  日期：——
• Remote asymmetric induction in diastereoface selective addition reactions of optically active .alpha.-substituted-.beta.-silyl (E)-hexenoates with achiral .alpha.-alkoxy and .beta.-alkoxy acetals
  作者：James S. Panek、Michael Yang

  DOI：10.1021/jo00020a009

  日期：1991.9

  Optically active and diastereomerically pure (E)-crotylsilanes 1 function as effective chiral carbon nucleophiles in trimethylsilyl trifluoromethanesulfonate (TMSOTf) catalyzed asymmetric addition reactions of achiral, alpha-alkoxy and beta-alkoxy acetals 2, resulting in the highly diastereo- and enantioselective construction of homoallylic ethers with excellent levels of 1,4- and 1,5-asymmetric induction.
• Direct Amino-Crotylsilylation of Achiral Acetals and Aldehydes: Asymmetric Synthesis of Homoallylic Amines and Functionalized Pyrrolidines
  作者：James S. Panek、Nareshkumar F. Jain

  DOI：10.1021/jo00089a004

  日期：1994.5

  The condensation between chiral (E)-crotyl-silanes 1 and in situ-generated achiral N-acylimines produces homoallylic N-acylamines 3 or tetrasubstituted N-acylpyrrolidines 4 with high levels of diastereoselection.
• Conjugate addition reactions of chiral (E)-crotylsilanes: application to an asymmetric [3 + 2] cyclopentane annulation
  作者：James S. Panek、Nareshkumar F. Jain

  DOI：10.1021/jo00061a001

  日期：1993.4

  Functionalized (E)-crotylsilanes 1 undergo Lewis acid promoted conjugate addition reactions with alpha-substituted enals and methyl vinyl ketone 2 to produce tetrasubstituted cyclopentanes 3 with high levels of diastereoselection. The reaction is believed to proceed by an initial 1,4-addition which is followed by a 1,2-silyl migration and a final cyclization step involving the derived boron enolate resulting in the construction of the cyclopentanoid product.