Methyl (E)-3-<(3R,7aS)-2-phenylperhydropyrrolo<1,2-c>imidazol-3-yl>propenoate | 71464-77-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: Methyl (E)-3-<(3R,7aS)-2-phenylperhydropyrrolo<1,2-c>imidazol-3-yl>propenoate
• 英文别名: methyl (E)-3-[(3R,7aS)-2-phenyl-1,3,5,6,7,7a-hexahydropyrrolo[1,2-c]imidazol-3-yl]prop-2-enoate
• CAS: 71464-77-2
• 化学式: C₁₆H₂₀N₂O₂
• 分子量: 272.347
• InChiKey: FVEHPIDUYIETFD-LWLVDVGCSA-N

物化性质

• 沸点：
  395.8±37.0 °C(predicted)
• 密度：
  1.19±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  32.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl (E)-3-<(3R,7aS)-2-phenylperhydropyrrolo<1,2-c>imidazol-3-yl>propenoate 在 copper(l) iodide 三氟化硼乙醚 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 methyl (3S)-3-(1,3-dithian-2-yl)-4-methylpentanoate
  参考文献：
  名称：

  Synthetic studies on biscembranoids: asymmetric total synthesis of methyl sarcoate

  摘要：

  The asymmetric total synthesis of a marine natural product, methyl sarcoate, has been achieved featuring the asymmetric Michael addition, the dithiane coupling, the Kosugi-Migita-Stille coupling, and the ring-closing metathesis. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2004.12.132

文献信息

• Asymmetric Cycloaddition of<i>N</i>-Metalated Azomethine Ylides with the Optically Active α,β-Unsaturated Esters Derived from α-Amino Acids
  作者：Shuji Kanemasa、Hidetoshi Yamamoto、Eiji Wada、Tosio Sakurai、Kunio Urushido

  DOI：10.1246/bcsj.63.2857

  日期：1990.10

  α,β-Unsaturated esters bearing a chiral oxazolidine or perhydropyrrolo[1,2-c]imidazole auxiliary at the β-position have been prepared and applied to the cycloadditions with N-metalated azomethine ylides derived from α-(benzylideneamino) esters. These reactions are found to proceed with an exclusively high diastereofacial selectivity to give 2,4-pyrrolidinedicarboxylates with four consecutive chiral

  已经制备了在 β 位带有手性恶唑烷或全氢吡咯并 [1,2-c] 咪唑助剂的 α,β-不饱和酯，并将其应用于与衍生自 α-（亚苄基氨基）酯的 N-金属化偶氮甲碱叶立德的环加成反应。发现这些反应以独特的高非对映选择性进行，在去除手性助剂后得到具有四个连续手性中心的 2,4-吡咯烷二羧酸盐。讨论了过渡态的详细立体化学。
• Asymmetric Michael Addition of the<i>N</i>-Alkylidene Derivative of an α-Amino Ester to Methyl (<i>E</i>)-3-[(3<i>R</i>,7a<i>S</i>)-2-Phenylperhydropyrrolo[1,2-<i>c</i>]imidazol-3-yl]propenoate
  作者：Hidetoshi Yamamoto、Shuji Kanemasa、Eiji Wada

  DOI：10.1246/bcsj.64.2739

  日期：1991.9

  The exclusively diastereoselective asymmetric Michael addition of the lithiated methyl N-(2,2-dimethylpropylidene)glycinate to methyl (E)-3-[(3R,7aS)-2-phenylperhydropyrrolo[1,2-c]imidazol-3-yl]propenoate is described. The synperiplanar conformer of the acceptor propenoate participated in the reaction where the re-face of the acceptor molecule was attacked by the re(β)-face of the lithiated intermediate.

  报道了锂化的甲基N-(2,2-二甲基丙叉)甘氨酸酯与甲基(E)-3-[(3R,7aS)-2-苯基全氢吡咯[1,2-c]咪唑-3-基]丙烯酸酯之间的专一性立体选择性不对称迈克尔加成反应。在这种反应中，受体的烯丙酸酯的同侧平伏构象参与反应，其中受体分子的re面被锂化中间体的re(β)面攻击。
• Asymmetric 1,3-dipolar cycloadditions of azomethine ylides with a chiral electron-deficient olefinic dipolarophile
  作者：Kanemasa Shuji、Yamamoto Hidetoshi

  DOI：10.1016/s0040-4039(00)94463-0

  日期：1990.1

  The first example of efficient asymmetric 1,3-dipolar cycloadditions of azomethine ylides is presented, where reactive N-metalated azomethine ylides and the α,β-unsaturated ester with a chiral perhydropyrrolo[1,2—c]imidazol-3-yl moiety at the β-position have been employed. The exclusive participation of thermodynamically less stable 3-H/3′-H synperiplanar conformer is based on its sterical preference

  给出了高效有效的不对称1,3-偶极偶氮甲亚胺环加成反应的第一个例子，其中反应性N-金属化的偶氮甲亚胺和具有手性过氢吡咯并[1,2 - c ]咪唑-3-基的α，β-不饱和酯在β-位已被采用。热力学不稳定的3-H / 3'-H上平面共形异构体的排他性参与是基于其在边界轨道和螯合控制的刚性游离态中的空间偏好。
• Asymmetric Dipolar Cycloaddition of Nitrile Oxides to the α,β-Unsaturated Esters Bearing an Imidazolidine Chiral Controller at the β-Position
  作者：Shuji Kanemasa、Takashi Hayashi、Hidetoshi Yamamoto、Eiji Wada、Tosio Sakurai

  DOI：10.1246/bcsj.64.3274

  日期：1991.11

  Some α,β-unsaturated esters bearing an imidazolidine chiral controller at the β-position were employed in the asymmetric cycloaddition to nitrile oxides. Regio- and diastereoselectivities were both poor when the chiral controller was a perhydropyrrolo[1,2-c]imidazol-3-yl auxiliary, while the reaction of the esters bearing a C2-symmetric imidazolidine chiral controller was exclusively regioselective or diastereoselective depending upon the nature of N-substituent. The transition state was briefly discussed.

  一些在 β 位带有咪唑烷手性控制剂的 α,β-不饱和酯被用于与腈氧化物的不对称环加成反应。当手性控制剂是全氢吡咯并[1,2-c]咪唑-3-基助剂时，区域选择性和非对映选择性都很差，而带有C2对称咪唑烷手性控制剂的酯的反应完全是区域选择性或非对映选择性，具体取决于N-取代基的性质。简要讨论了过渡状态。
• ASYMMETRIC SYNTHESIS OF 3-ALKYLSUCCINALDEHYDIC ACID METHYL ESTERS
  作者：Masatoshi Asami、Teruaki Mukaiyama

  DOI：10.1246/cl.1979.569

  日期：1979.5.5

  The highly stereoselective Michael addition was achieved by treating an aminal, prepared from (S)-2-(anilinomethyl)pyrrolidine and fumaraldehydic acid methyl ester, with the Grignard reagents. 3-Alkylsuccinaldehydic acid methyl esters were obtained with high enantiomeric excesses by the hydrolysis of the resulting aminals.

  高度立体选择性迈克尔加成是通过用格氏试剂处理由（S）-2-（苯胺基甲基）吡咯烷和富马醛酸甲酯制备的胺醛实现的。3-烷基琥珀醛酸甲酯是通过水解所得缩醛胺获得的，对映体过量。