(5R,6S,3E)-methyl-5-methyl-6-(N-methylcarbamate)-6-phenyl-hexenoate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (5R,6S,3E)-methyl-5-methyl-6-(N-methylcarbamate)-6-phenyl-hexenoate
• 英文别名: (5R,6S,3E)-methyl 5-methyl-6-(N-methylcarbamate)-6-phenylhexenoate；methyl (E,5R,6S)-6-(methoxycarbonylamino)-5-methyl-6-phenylhex-3-enoate
• 化学式: C₁₆H₂₁NO₄
• 分子量: 291.347
• InChiKey: RZMMYIXOABOGTO-UJOIQMEZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  甲氧羰基亚甲基三苯基正膦 、 (5R,6S,3E)-methyl-5-methyl-6-(N-methylcarbamate)-6-phenyl-hexenoate 在 臭氧 作用下， 生成 (4R,5S,2E)-methyl 5-((methoxycarbonyl)amino)-4-methyl-5-phenylpent-2-enoate
  参考文献：
  名称：

  从手性硅烷加成到原位生成的N-酰基亚胺离子中的双功能均烯丙基氨基甲酸酯

  摘要：

  利用新型手性硅烷，通过路易斯酸促进的不对称氨基丙烯酰化反应，分别生成了带有α，β-不饱和酯或烯丙基碳酸酯的均烯丙基氨基甲酸酯。这些双功能结构单元可以进一步进行迈克尔加成或环化，以选择性地形成功能化的内酰胺，氮杂环丁烷和四氢嘧啶酮。

  DOI：

  10.1021/ol301428y
• 作为产物：
  描述：

  (2S,3R,4S,5S)-3-(dimethylphenyl)silane-4-methyl-5-phenyl-pyrrolidine-N-methylcarbamate-2-acetic acid methyl ester 在 三氟化硼乙醚 作用下， 生成 (5R,6S,3E)-methyl-5-methyl-6-(N-methylcarbamate)-6-phenyl-hexenoate
  参考文献：
  名称：

  Direct Amino-Crotylsilylation of Achiral Acetals and Aldehydes: Asymmetric Synthesis of Homoallylic Amines and Functionalized Pyrrolidines

  摘要：

  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.

  DOI：

  10.1021/jo00089a004

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。
• Three-Component, Room Temperature Crotylation Catalyzed by Solid-Supported Brønsted Acid:  Enantioselective Synthesis of Homoallylic Carbamates
  作者：Darren J. Lipomi、James S. Panek

  DOI：10.1021/ol051885s

  日期：2005.10.1

  A heterogeneous, three-component crotylation of in situ generated N-acyl iminium ions has been developed. This reaction proceeds under ambient temperature in MeCN and is catalyzed by macroporous polystyrene-bound sulfonic acid (MP-TsOH). Workup is accomplished by filtration, upon which the catalyst is recoverable. A range of homoallylic amine equivalents have been prepared from the corresponding aldehydes, carbamates, and chiral (E)-crotylsilanes in a highly stereoselective manner.
• Bifunctional Homoallylic Carbamates from Chiral Silane Additions to in Situ Generated <i>N</i>-Acyl Iminium Ions
  作者：Jie Wu、Kai-Cheng Zhu、Ping-Wei Yuan、James S. Panek

  DOI：10.1021/ol301428y

  日期：2012.7.20

  Homoallylic carbamates bearing an α,β-unsaturated ester or an allylic carbonate were generated respectively utilizing novel chiral silanes through Lewis acid promoted asymmetric aminocrotylation. Those bifunctional building blocks could further undergo Michael addition or cyclization to selectively form functionalized lactams, azetidines, and tetrahydropyrimidinones.

  利用新型手性硅烷，通过路易斯酸促进的不对称氨基丙烯酰化反应，分别生成了带有α，β-不饱和酯或烯丙基碳酸酯的均烯丙基氨基甲酸酯。这些双功能结构单元可以进一步进行迈克尔加成或环化，以选择性地形成功能化的内酰胺，氮杂环丁烷和四氢嘧啶酮。
• 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.