(+/-)-1,1'-(1-N,N-dimethylaminopropane-1,3-diyl)ferrocene | 64440-46-6

• 英文名称: (+/-)-1,1'-(1-N,N-dimethylaminopropane-1,3-diyl)ferrocene
• 英文别名: 1'-dimethylamino[3]ferrocenophane
• CAS: 64440-46-6；51920-92-4；51839-59-9
• 化学式: C₁₅H₁₉FeN
• 分子量: 269.17
• InChiKey: AEZMBMCVYZGCPS-RSAXXLAASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (+/-)-1,1'-(1-N,N-dimethylaminopropane-1,3-diyl)ferrocene 在 L-酒石酸 、 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 以2.1 g的产率得到R(+)-1'-dimethylamino[3]ferrocenophane
  参考文献：
  名称：

  基于二茂铁oph烷的双功能有机催化剂，用于高度对映选择性迈克尔反应

  摘要：

  乙酰丙酮和之间高度对映选择性迈克尔反应反式-β-nitroolefins通过新颖的基于二茂铁基叔胺-硫脲有机催化剂，以提供良好的相应产品，以优异的产率（高达95％）和对映选择性（高达99％实现EE） 。

  DOI：

  10.1016/j.tet.2018.06.036
• 作为产物：
  描述：

  、 二甲胺 在 三乙胺 作用下， 以 甲醇 为溶剂， 以1.21 g的产率得到(+/-)-1,1'-(1-N,N-dimethylaminopropane-1,3-diyl)ferrocene
  参考文献：
  名称：

  基于二茂铁oph烷的双功能有机催化剂，用于高度对映选择性迈克尔反应

  摘要：

  乙酰丙酮和之间高度对映选择性迈克尔反应反式-β-nitroolefins通过新颖的基于二茂铁基叔胺-硫脲有机催化剂，以提供良好的相应产品，以优异的产率（高达95％）和对映选择性（高达99％实现EE） 。

  DOI：

  10.1016/j.tet.2018.06.036

文献信息

• Isomeric diphosphines of a heteroannularly bridged ferrocene: preparation, chromatographic separation and structure elucidation
  作者：Georg Kutschera、Christoph Kratky、Walter Weissensteiner、Michael Widhalm

  DOI：10.1016/0022-328x(95)05849-k

  日期：1996.2

  chromatography. Their substitution pattern was elucidated X-ray structure analyses and chemical correlation. Corresponding diphosphines 10a–10d were derived with moderate yields via acetates 8a–8d. A search for stable conformers of 7a–7d and 11 was conducted using empirical force field calculations. Calculated minimum-energy geometries were compared with crystal structures of 7a, 7c and 7d.

  异环桥联的氨基膦5的两次锂化产生了五个异构的氨基二膦7a-7d和11的混合物，它们通过吸附色谱法分离。他们的替代模式被阐明了X射线结构分析和化学相关性。相应的二膦10a–10d通过乙酸盐8a–8d以中等收率得到。使用经验力场计算对7a–7d和11的稳定构象异构体进行了搜索。将计算出的最小能量几何形状与7a，7c和7d的晶体结构进行比较。
• Structural Features of Lithio[3]ferrocenophane Systems Bearing Stabilizing Dimethylamino Substituents
  作者：Chao Chen、Roland Fröhlich、Gerald Kehr、Gerhard Erker

  DOI：10.1021/om8001894

  日期：2008.7.1

  to form a (13·n-BuLi) dimer that was also characterized by X-ray diffraction. Directed lithiation of the nonbridged ferrocene derivative 1-(dimethylaminobenzyl)ferrocene (16) with tert-butyllithium resulted in an opposite stereoselectivity to yield (R*,p-R*)-17, which forms a chiral dimeric structure in the solid state, as was revealed by its X-ray crystal structure analysis.

  用正丁基锂处理α-二甲基氨基[3]二茂铁oph烷衍生物3导致在二茂铁单元的相邻Cp环上进行定向o-金属化反应，以选择性地产生（R *，R *，p - S *）非对映异构体4。类似地，rac - 12的锂化得到（R *，p - S *）- 13。这两种化合物均在晶体中形成以中心C 2 Li 2四元环部分为特征的内消旋型二聚体。化合物13用过量的正丁基锂结晶，形成（13 · n -BuLi）二聚体，该二聚体也通过X射线衍射表征。非桥二茂铁衍生物1-（二甲基氨基苄基）二茂铁（16）与叔丁基锂的直接锂化反应产生相反的立体选择性，生成（R *，p - R *）- 17，形成固态的手性二聚体结构，如通过X射线晶体结构分析所揭示的那样。
• Monocyclopentadienylhydride Derivatives of Ruthenium:  Stereoselective Proton Transfer and Proton-Hydride Exchange in an Extremely Short Dihydrogen Bond
  作者：Ester Cayuela、Félix A. Jalón、Blanca R. Manzano、Gustavo Espino、Walter Weissensteiner、Kurt Mereiter

  DOI：10.1021/ja031926k

  日期：2004.6.1

  Diastereomerically pure complexes of formula CpRuCl(PP*) and CpRuH(PP*) with chiral ferrocenyl diphosphines were prepared and the selectivity of proton-transfer processes over the monohydride compounds with different acids was studied. With 1 equiv of HBF4 the cis-dihydrogen and trans-dihydride complexes were formed while with 3 equiv of CF3CO2H the trans-dihydride derivative was the only product. However, the use of 1 equiv of CF3CO2H led to a dihydrogen bonded complex with an extremely short RuH...HO2CF3 interaction that exhibits proton-hydride exchange. Using the labeled acid CF3CO2D, a stereoselective transference of the deuteron was demonstrated that implies the previous epimerization of the monohydride and the subsequent attack of the acid in the position previously occupied by the hydride.
• Asymmetric cyclopalladation of 1′-dimethylamino-[3] ferrocenophane: central and planar chirality and the effect of conformational rigidity
  作者：V.I. Sokolov、L.L. Troitskaya、B. Gautheron、G. Tainturier

  DOI：10.1016/s0022-328x(00)96090-x

  日期：1982.9
• Synthesis and molecular structure of enantiopure 1-(diphenylphosphino)-2,1′-[(1-N,N-dimethylamino)-1,3-propanediyl]-ferrocene and its palladium dichloride complex, a new ligand for enantioselective catalysts
  作者：Alexander Mernyi、Christoph Kratky、Walter Weissensteiner、Michael Widhalm

  DOI：10.1016/0022-328x(95)05850-o

  日期：1996.2

  The palladium dichloride complex of (S-c, S-m)-1-(diphenylphosphino)-2,1'-[(1-N,N-dimethylamino)-1,3-propanediyl]-ferrocene (5-PdCl2) has been prepared from enantiopure (S)-1,1'-[(1-N,N-dimethylamino)-1,3-propanediyl]-ferrocene (4) via a highly stereoselective ortho-lithiation followed by reaction with chlorodiphenyl phosphine to give amino phosphine 5, which on treatment with (CH3CN)(2)PdCl2 gave the complex 5-PdCl2. The absolute configuration of the (-)(589)-enantiomer of 4 was deduced from the X-ray structure of its tartrate confirming (S)-configuration at the stereogenic center. A conformational analysis including X-ray structure analysis of 5 and 5-PdCl2 as well as empirical force field calculations on 4 and 5 together with NMR data shows strong stereochemical similarities of 5 and 5-PdCl2 with the widely used ligand PPFA and its palladium dichloride complex PPFA-PdCl2.