(1R,3aR,6aR)-octahydro-1-pentalenyl 2,4-dinitrobenzoate | 177600-48-5

• 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: (1R,3aR,6aR)-octahydro-1-pentalenyl 2,4-dinitrobenzoate
• CAS: 177600-48-5
• 化学式: C₁₅H₁₆N₂O₆
• 分子量: 320.302
• InChiKey: ZVFAXFAUBWAXSJ-UDZFHETQSA-N

物化性质

• 沸点：
  464.1±30.0 °C(Predicted)
• 密度：
  1.40±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.24
• 重原子数：
  23.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  112.58
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (1R,3aR,6aR)-octahydro-1-pentalenyl 2,4-dinitrobenzoate 在 氢氧化钾 、 三苯基膦 、 三氟乙酸 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 68.17h， 生成 N-[(1S,3aR,6aR)-octahydro-1-pentalenyl]-4-methylbenzenesulfonamide
  参考文献：
  名称：

  α-Lithiation-rearrangement of N-toluenesulfonyl aziridines with sec-butyllithium and (−)-sparteine: opposite sense of asymmetric induction to epoxides

  摘要：

  The alpha-lithiation rearrangement of three cyclic N-toluenesulfonyl (tosyl) aziridines has been carried out using sec-butyl-lithium/(-)-sparteine. In each case, it was established that preferential lithiation of the S-aziridine stereocentre occurred. This is the opposite sense of asymmetric induction to that observed with epoxides. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01677-0
• 作为产物：
  描述：

  氧化环辛烯 在 仲丁基锂 、 三苯基膦 、 鹰爪豆碱 、 偶氮二甲酸二乙酯 作用下， 以 乙醚 为溶剂， 反应 65.0h， 生成 (1R,3aR,6aR)-octahydro-1-pentalenyl 2,4-dinitrobenzoate
  参考文献：
  名称：

  α-Lithiation-rearrangement of N-toluenesulfonyl aziridines with sec-butyllithium and (−)-sparteine: opposite sense of asymmetric induction to epoxides

  摘要：

  The alpha-lithiation rearrangement of three cyclic N-toluenesulfonyl (tosyl) aziridines has been carried out using sec-butyl-lithium/(-)-sparteine. In each case, it was established that preferential lithiation of the S-aziridine stereocentre occurred. This is the opposite sense of asymmetric induction to that observed with epoxides. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)01677-0

文献信息

• On the α-lithiation-rearrangement of N-toluensulfonyl aziridines: mechanistic and synthetic aspects
  作者：Peter O'Brien、Clare M Rosser、Darren Caine

  DOI：10.1016/j.tet.2003.09.024

  日期：2003.12

  can then partition through two pathways: (i) rearrangement to allylic or bicyclic sulfonamides via C–H insertion reactions or (ii) reductive alkylation to alkenes via attack by sec-butyllithium and subsequent elimination of TsNH2. In the (−)-sparteine reactions, the products were generated with 38–66% ee and the sense of asymmetric induction involved lithiation of the S-aziridine stereocentre. This is

  进行了详细的研究，使用仲丁基锂（有和没有添加（-）-天冬氨酸和TMEDA等配体）对五个环烯N-甲苯磺酰基（甲苯磺酰基）氮丙啶进行重排。烯丙基磺酰胺是环戊烯和环己烯氮丙啶的主要产物，而双环磺酰胺是从环庚烯和环辛烯氮丙啶获得的。在大多数情况下，对甲苯磺酰胺（TsNH 2）作为副产品生产，并就其形成机理进行了机械解释。据信，这些反应涉及α-锂化为锂化的氮丙啶，然后可以通过两个途径分配：（i）通过CH插入反应重排为烯丙基或双环磺酰胺，或（ii）通过仲丁基锂的攻击而还原为烷基化为烯烃。和随后消除TsNH 2。在（-）-天冬氨酸反应中，生成的产物的ee为38-66％，不对称感应的感觉涉及S-氮丙啶立体中心的锂化。这与用环氧化物观察到的相反。
• Evaluation of (+)-Sparteine-like Diamines for Asymmetric Synthesis
  作者：Michael J. Dearden、Matthew J. McGrath、Peter O'Brien

  DOI：10.1021/jo049182w

  日期：2004.8.1

  Three new (+)-sparteine-like diamines were prepared from (-)-cytisine and evaluated as sparteine surrogates in the alpha-lithiation rearrangement of cyclooctene oxide and the palladium(II)/diamine catalyzed oxidative kinetic resolution of I-indanol. The new diamines exhibited opposite enantioselectivity to that observed with (-)-sparteine but increasing the steric hindrance of the N-alkyl group beyond N-Et had a detrimental effect on enantioselectivity. The optimal N-Me diamine was evaluated with much success in five other (-)-sparteine-mediated processes involving different metals (lithium, magnesium, and copper) and different types of reaction mechanisms.
• A Readily-Accessible (+)-Sparteine Surrogate
  作者：Michael J. Dearden、Catherine R. Firkin、Jean-Paul R. Hermet、Peter O'Brien

  DOI：10.1021/ja027774v

  日期：2002.10.1

  A "(+)-sparteine-like" chiral diamine, readily synthesized in three steps from (-)-cytisine, has been evaluated in four different asymmetric transformations; in each case, selectivity in an enantiocomplementary fashion to (-)-sparteine was observed.