(2S)-1-(cyclopenten-1-yl)-2-(methoxymethyl)pyrrolidine | 129967-93-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (2S)-1-(cyclopenten-1-yl)-2-(methoxymethyl)pyrrolidine
• CAS: 129967-93-7
• 化学式: C₁₁H₁₉NO
• 分子量: 181.278
• InChiKey: AVQUUUNXIFUKEI-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  乙基叠氮基甲酸酯 、 (2S)-1-(cyclopenten-1-yl)-2-(methoxymethyl)pyrrolidine 生成 ethyl (2S)-2-(methoxymethyl)pyrrolidine-1-carboxylate
  参考文献：
  名称：

  Stereoselective azide cycloaddition to chiral cyclopentanone enamines

  摘要：

  The enamine derived from cyclopentanone and (2R,5R)-2,5-bis(methoxymethyl)pyrrolidine added ethyl N-mesylazidoformimidate [N3C(OEt)NMs] and ethyl azidoformate (N3CO2Et) with high asymmetric induction (>95%), while the corresponding cyclohexanone enamine gave ring contraction products. With the same azides the cyclopentanone enamine, prepared from (S)-2-(methoxymethyl)pyrrolidine gave N-substituted alpha-amino cyclopentanones in moderate enantiomeric excess. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00239-5
• 作为产物：
  描述：

  (S)-(+)-2-(甲氧基甲基)吡唑烷 、 环戊酮 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 5.0h， 生成 (2S)-1-(cyclopenten-1-yl)-2-(methoxymethyl)pyrrolidine
  参考文献：
  名称：

  Stereoselective azide cycloaddition to chiral cyclopentanone enamines

  摘要：

  The enamine derived from cyclopentanone and (2R,5R)-2,5-bis(methoxymethyl)pyrrolidine added ethyl N-mesylazidoformimidate [N3C(OEt)NMs] and ethyl azidoformate (N3CO2Et) with high asymmetric induction (>95%), while the corresponding cyclohexanone enamine gave ring contraction products. With the same azides the cyclopentanone enamine, prepared from (S)-2-(methoxymethyl)pyrrolidine gave N-substituted alpha-amino cyclopentanones in moderate enantiomeric excess. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00239-5

文献信息

• [3 + 3]-Carbocyclizations of nitroallylic esters and enamines with stereoselective formation of up to six new stereogenic centers
  作者：Dieter Seebach、Martin Missbach、Giorgio Calderari、Martin Eberle

  DOI：10.1021/ja00177a026

  日期：1990.10

  and intermediates, which can be trapped under certain conditions, as well as previous investigations of single steps of the in situ reaction sequence involved in the carbocyclization are used to arrive at a tentative proposal for the steric course of these steps: (i) intermolecular coupling of the trigonal centers of enamine and nitroolefin with preferred relative topicity like, (ii) intramolecular coupling

  讨论了导致观察到的产物的复杂反应序列的机制。可以在某些条件下捕获的产物和中间体的结构，以及先前对参与碳环化的原位反应序​​列的单个步骤的研究，用于得出这些步骤的空间过程的初步建议： (i) 烯胺和硝基烯烃的三角中心的分子间偶联，具有优选的相对局部性，(ii) 中间体烯胺中的三角中心的分子内偶联，(iii) 硝基阴离子部分的质子化，和 (iv) 的质子化烯胺（在单环产品的情况下）
• β,β‘- and α,β,β‘-Annulation Reactions of Cyclic Enamines:  Enantioselective Synthesis of Bicyclo[3.<i>n</i>.1]alkenones (<i>n</i> = 2, 3) and Tricyclo[3.3.0.0^2,8]octanes from Fischer Alkenyl Carbene Complexes
  作者：José Barluenga、Alfredo Ballesteros、Javier Santamaría、Ramón Bernardo de la Rúa、Eduardo Rubio、Miguel Tomás

  DOI：10.1021/ja002905i

  日期：2000.12.1
• Group 6 Heteroatom- and Non-Heteroatom-Stabilized Carbene Complexes. β,β‘- and α,β,β‘-Annulation Reactions of Cyclic Enamines
  作者：José Barluenga、Alfredo Ballesteros、Ramón Bernardo de la Rúa、Javier Santamaría、Eduardo Rubio、Miguel Tomás

  DOI：10.1021/ja0278077

  日期：2003.2.19

  Cyclization reactions of group 6 Fischer carbene complexes with cyclopentanone and cyclohexanone enamines are described. Enamine 3a undergoes thermal alpha,beta,beta'-annulation with alkenylcarbene complexes 1 and 2 (THF, 60degreesC), affording semibullvalenes 5. The metalate intermediates 6, resulting from beta,beta'-annulation of the enamines 3a and 4a, were quantitatively formed by running the reaction in hexane at room temperature. Acid-promoted demetalation of 6 afforded endo-2-bicyclo[3.2.1]octen-8-ones 7 and endolexo-2-bicyclo[3.3.1]nonen-9-ones 8 (endolexo = 5:1). Using (S)-methoxymethylpyrrolidine-derived enamines 3b and 4b,c allowed highly enantioenriched cycloadducts endo-(+)-7 as well as endo(-)-8 and exo-(-)-8 to be accessed. The non-heteroatom-stabilized carbene complex 10 was formed from complex 6 by Me3SiOTf-promoted elimination of the methoxy group, characterized by C-13 NMR, and transformed into the organic compounds 7, 7-d, and 11 as well as into bicyclo[3.2.1]octan-2,8-diones 14 and cycloheptanones 15. On the basis of this sequence, enantioenriched cycloheptanones (+)-15 were efficiently prepared in one pot from carbene complexes 2 and enamine 3b (51-55% yield, 91-96% ee). Extension of this work to simple Fischer carbene complexes 16 allowed an appropriate way to generate the nonstabilized pentacarbonyl[(phenyl(alkyl)carbene]tungsten complex 17 to be designed, for which the thermal and chemical behavior leading to compounds 18-21 is described.
• BLARER, S. J.;SCHWEIZER, W. B.;SEEBACH, D., HELV. CHIM. ACTA, 1982, 65, N 5, 1637-1654
  作者：BLARER, S. J.、SCHWEIZER, W. B.、SEEBACH, D.

  DOI：——

  日期：——
• Stereoselective azide cycloaddition to chiral cyclopentanone enamines
  作者：Stefania Fioravanti、Lucio Pellacani、Damiano Ricci、Paolo A Tardella

  DOI：10.1016/s0957-4166(97)00239-5

  日期：1997.7

  The enamine derived from cyclopentanone and (2R,5R)-2,5-bis(methoxymethyl)pyrrolidine added ethyl N-mesylazidoformimidate [N3C(OEt)NMs] and ethyl azidoformate (N3CO2Et) with high asymmetric induction (>95%), while the corresponding cyclohexanone enamine gave ring contraction products. With the same azides the cyclopentanone enamine, prepared from (S)-2-(methoxymethyl)pyrrolidine gave N-substituted alpha-amino cyclopentanones in moderate enantiomeric excess. (C) 1997 Elsevier Science Ltd.