(+)-N-isopropyl-decahydro-1,5-methano-pyrido[1,2-a][1,5]diazocine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 英文名称: (+)-N-isopropyl-decahydro-1,5-methano-pyrido[1,2-a][1,5]diazocine
• 英文别名: (1R,2S,9S)-11-propan-2-yl-7,11-diazatricyclo[7.3.1.02,7]tridecane
• 化学式: C₁₄H₂₆N₂
• 分子量: 222.374
• InChiKey: GDAXMBNDFLATNO-MCIONIFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  cytisine 在 platinum(IV) oxide lithium aluminium tetrahydride 、 氢气 、 sodium triacetoxyborohydride 、 溶剂黄146 作用下， 以 四氢呋喃 为溶剂， 反应 62.0h， 生成 (+)-N-isopropyl-decahydro-1,5-methano-pyrido[1,2-a][1,5]diazocine
  参考文献：
  名称：

  使用 (-)-Cytisine 衍生物对前手性膦进行去对称化

  摘要：

  y历史上，(-)-sparteine-sec-BuLi 已被用于去对称化前手性膦。在这份报告中，从 Laburnum anagyro-ides 种子中提取的生物碱衍生物已被用来模拟 (+)-sparteine，这是不容易获得的。在一些情况下，在烷基取代（以及芳基取代）前手性膦衍生物的去质子化过程中，使用 (+)-Sparteine 替代物实现的对映选择性优于 (-)-sparteine 本身。此外，这些替代物的使用为磷化学中的手性转换提供了一种新方法。((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)。

  DOI：

  10.1002/ejoc.200400006

文献信息

• Desymmetrization of Prochiral Phosphanes Using Derivatives of (−)-Cytisine
  作者：Magnus J. Johansson、Lennart O. Schwartz、Mohamed Amedjkouh、Nina C. Kann

  DOI：10.1002/ejoc.200400006

  日期：2004.5

  yHistorically, (-)-sparteine-sec-BuLi has been used to desym-metrize prochiral phosphanes. In this report, derivatives of an alkaloid extracted from the seeds of Laburnum anagyro-ides have been utilized to mimic (+)-sparteine, which is not readily available. In several cases, the enantioselectivities achieved with the (+)-Sparteine surrogates outperformed (-)-sparteine itself in the deprotonation of

  y历史上，(-)-sparteine-sec-BuLi 已被用于去对称化前手性膦。在这份报告中，从 Laburnum anagyro-ides 种子中提取的生物碱衍生物已被用来模拟 (+)-sparteine，这是不容易获得的。在一些情况下，在烷基取代（以及芳基取代）前手性膦衍生物的去质子化过程中，使用 (+)-Sparteine 替代物实现的对映选择性优于 (-)-sparteine 本身。此外，这些替代物的使用为磷化学中的手性转换提供了一种新方法。((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)。
• An Experimental and Computational Study of the Enantioselective Lithiation of <i>N</i>-Boc-pyrrolidine Using Sparteine-like Chiral Diamines
  作者：Peter O'Brien、Kenneth B. Wiberg、William F. Bailey、Jean-Paul R. Hermet、Matthew J. McGrath

  DOI：10.1021/ja046834p

  日期：2004.12.1

  The enantioselective lithiation of N-Boc-pyrrolidine using sec-butyllithium and isopropyllithium in the presence of sparteine-like diamines has been studied experimentally and computationally at various theoretical levels through to B3P86/6-31G*. Of the (-)-cytisine-derived diamines (N-Me, N-Et, N-Bu-n, N-CH2t-Bu, N-Pr-i) studied experimentally, the highest enantioselectivity (er 95:5) was observed with the least sterically hindered N-Me-substituted diamine, leading to preferential removal of the pro-R proton i.e., opposite enantioselectivity to (-)-sparteine. The experimental result with the N-Me-substituted diamine correlated well with the computational results: at the B3P86/6-31G* level, the sense of induction was correctly predicted; the lowest energy complex of isopropyllithium/diamine/N-Boc-pyrrolidine also had the lowest activation energy (DeltaH(double dagger) = 11.1 kcal/mol, DeltaG(double dagger) = 11.5 kcal/mol) for proton transfer. The computational results with the N-Pr-i-substituted diamine identified a transition state for proton transfer with activation energies of DeltaH(double dagger) = 11.7 kcal/mol and DeltaG(double dagger) = 11.8 kcal/mol (at the B3P86/6-31G* level). Although comparable to (-)-sparteine and the N-Me-substituted diamine, these DeltaH(double dagger) and DeltaG(double dagger) values are at odds with the experimental observation that use of the N-Pr-i-substituted diamine gave no product. It is suggested that steric crowding inhibits formation of the prelithiation complex rather than increasing the activation enthalpy for proton transfer in the transition state. Three other ligands (N-H and O-substituted as well as a five-membered ring analogue) were studied solely using computational methods, and the results predict that the observed enantioselectivity would be modest at best.
• New chiral amine ligands in the desymmetrization of prochiral phosphine boranes
  作者：Magnus J. Johansson、Lennart Schwartz、Mohamed Amedjkouh、Nina Kann

  DOI：10.1016/j.tetasy.2004.09.023

  日期：2004.11

  phosphine ligands can be prepared via desymmetrization of prochiral phosphine boranes using s-BuLi·(−)-sparteine complexes. One limitation of this method, however, has been that (+)-sparteine is not easily accessible. Herein, we show that derivatives of another alkaloid, (−)-cytisine, are useful surrogates for (+)-sparteine in the desymmetrization of prochiral phenyl-, cyclohexyl- and tert-butyl dimethyl

  可以使用s -BuLi·（-）-sparteine配合物通过前手性膦硼烷的不对称化来制备P-手性膦配体。然而，该方法的局限性在于不容易获得（+）-天冬氨酸。在本文中，我们显示了另一种生物碱（-）-胱氨酸的衍生物在前手性苯基-，环己基-和叔丁基二甲基膦硼烷的去对称化中，对于（+）-天冬氨酸是有用的替代物，最多可生成手性膦硼烷92％ee。还测试了其他手性二胺，但对映选择性不如（-）-胱氨酸衍生物高。