1,1′-bis[(tert-butoxycarbonyl)amino]ferrocene | 865444-44-6

• 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: 1,1′-bis[(tert-butoxycarbonyl)amino]ferrocene
• 英文别名: tert-butyl N-cyclopenta-1,3-dien-1-ylcarbamate;iron(2+)
• CAS: 865444-44-6
• 化学式: C₂₀H₂₈FeN₂O₄
• 分子量: 416.3
• InChiKey: SWASTLRZOOBTJR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  76.7
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,1′-bis[(tert-butoxycarbonyl)amino]ferrocene 在 甲醇 、 乙酰氯 作用下， 反应 2.5h， 以82%的产率得到1,1'-diaminoferrocene hydrochloride
  参考文献：
  名称：

  二茂铁桥联的双（咪唑啉-2-亚胺）配体的镍（II）和钯（II）配合物中的Ni-Fe和Pd-Fe相互作用

  摘要：

  双（咪唑啉-2-亚胺）配体N，N′-双（1,3-二异丙基-4,5-二甲基咪唑啉-2-亚胺基）-1,1'-二茂铁胺，fc（NIm）2（1）为准备好了。其与反应[的NiCl 2（DME）]（DME = 1,2-二甲氧基乙烷）或[的PdCl 2（MeCN中）2 ]，得到的四面体，顺磁性配合物[（1 -κ 2 Ñ，Ñ '）的NiCl 2（图6a）或抗磁，正方形平面配合物[（1 -κ 2 ñ，ñ '）的PdCl 2 ]（图6b）， 分别。对于后者，缓慢重排离子络合物[（1个-κFe，κ 2 Ñ，Ñ '）的PdCl]氯，[ 7 ]氯，观察到，随后通过1 H NMR和UV / Vis光谱。用NaBF 4处理[ 7 ] Cl得到[ 7 ] BF 4 ; 两个阳离子中的钯原子均采用具有短Fe-Pd键（约2.65Å）的正方形平面环境。此外，一系列的类型的双阳离子配合物[（1 -κFe，κ 2 Ñ，Ñ '）ML]（BF

  DOI：

  10.1021/acs.inorgchem.5b02457
• 作为产物：
  描述：

  1,1'-diisocyanatoferrocene 、 叔丁醇 以 乙醚 为溶剂， 反应 24.0h， 生成 1,1′-bis[(tert-butoxycarbonyl)amino]ferrocene
  参考文献：
  名称：

  Large-Scale Preparation of 1,1′-Ferrocenedicarboxylic Acid, a Key Compound for the Synthesis of 1,1′-Disubstituted Ferrocene Derivatives

  摘要：

  Efficient and simple methods for the large-scale preparation of 1,1'-ferrocenedicarboxylic acid, fc(COOH)2, involving the sodium salts of cyclopentadienecarboxylic methyl and ethyl esters, Na(C5H4COOR) (R = Me, Et), are presented. With fc(COOH)2 at hand, the syntheses of various 1,1'-disubstituted compounds of the type fcX(2) (X = CH2OH, COCl, CON3, NCO, NHCOOMe, NHBoc, NH2) were optimized and scaled up. The X-ray crystal structures of fc(COOEt)(2), fc(NCO)(2)center dot 1/2C(6)H(6), and fc(NHCOOMe)(2)center dot MeOH are reported.

  DOI：

  10.1021/om4004972

文献信息

• Hydrogen Isotope Exchange with Iridium(I) Complexes Supported by Phosphine-Imidazolin-2-imine P,N Ligands
  作者：Kristof Jess、Volker Derdau、Remo Weck、Jens Atzrodt、Matthias Freytag、Peter G. Jones、Matthias Tamm

  DOI：10.1002/adsc.201601291

  日期：2017.2.20

  phosphine‐imidazolin‐2‐imine RP,NR′ ligands (R=Ph, Cy, i‐Pr, t‐Bu; R′=Me, i‐Pr) were prepared from 1,2‐dibromobenzene by palladium‐catalyzed C–N coupling with 1,3,4,5‐tetramethylimidazolin‐2‐imine or 1,3‐diisopropyl‐4,5‐dimethylimidazolin‐2‐imine, followed by lithiation with tert‐butyllithium and reaction with the chlorophosphines (R2PCl). Their reaction with the dimeric iridium complex [Ir(cod)Cl]2 (cod=1

  由1,2-二溴苯制备苯撑桥杂膦-咪唑啉-2-亚胺R P，N R'配体（R = Ph，Cy，i- Pr，t- Bu; R'= Me，i- Pr）钯催化的C-N与1,3,4,5-四甲基咪唑啉-2-亚胺或1,3-二异丙基-4,5-二甲基咪唑啉-2-亚胺偶联，然后用叔丁基锂锂化并与叔丁基锂反应氯膦（R 2 PC1）。他们与二聚铱络合物[Ir（cod）Cl] 2（cod = 1,5-环辛二烯）的反应，随后与四[3,5-双（三氟甲基）苯基]硼酸钠（NaBArF 24）或六氟磷酸钾进行阴离子交换（KPF 6）分别提供了[[ R P，N R'）Ir（cod）] BArF 24或[[ R P，N R'）Ir（cod）] PF 6类型的铱配合物。后面的PF 6盐在结构上进行了表征，揭示了短的Ir-N键，可指示富电子的氮供体原子。测试了前一种配合物在催化H / D交换中的适用性。特别是具有配体t- Bu P，N
• Amino acid conjugates of 1,1′-diaminoferrocene. Synthesis and chiral organization
  作者：Somenath Chowdhury、Khaled A. Mahmoud、Gabriele Schatte、Heinz-Bernhard Kraatz

  DOI：10.1039/b506178d

  日期：——

  1,1′-Bis(tert-butoxycarbonylamino)ferrocene (6), a protected derivative of 1,1′-diaminoferrocene, has been synthesized by a very convenient method and serves as a synthon for 1,1′-diaminoferrocene. Its structure in solid state and in solution has been studied by NMR and X-ray crystallography. 1,1′-Bis(tert-butoxycarbonylamino)ferrocene serves as starting material for the synthesis of amino acid conjugates of L- and D-alanine. The structures of these bioconjugates have been studied by NMR and CD spectroscopy and X-ray crystallography and reveal that the chiral organization of the podant amino acid chains is controlled by the chirality of the attached amino acid. The substituents engage in strong intramolecular H-bonding generating 14-membered H-bonded rings, a motif previously unrealized in ferrocene–amino acid and peptide conjugates.

  1,1â²-双（叔丁氧羰基氨基）二茂铁（6）是 1,1â²-二氨基二茂铁的一种受保护衍生物，采用非常简便的方法合成，可作为 1,1â²-二氨基二茂铁的合成物。核磁共振和 X 射线晶体学对其固态和溶液结构进行了研究。1,1â²-双（叔丁氧羰基氨基）二茂铁是合成 L-和 D-丙氨酸氨基酸共轭物的起始原料。核磁共振、CD 光谱和 X 射线晶体学对这些生物共轭物的结构进行了研究，结果表明，荚膜氨基酸链的手性组织受控于所附氨基酸的手性。取代基在分子内发生强烈的氢键作用，生成 14 元氢键环，这种结构以前在二茂铁氨基酸和肽共轭物中从未出现过。
• Helically Chiral Peptides That Contain Ferrocene‐1,1′‐diamine Scaffolds as a Turn Inducer
  作者：Monika Kovačević、Ivan Kodrin、Sunčica Roca、Krešimir Molčanov、Yuning Shen、Bimalendu Adhikari、Heinz‐Bernhard Kraatz、Lidija Barišić

  DOI：10.1002/chem.201701602

  日期：2017.8

  by DFT studies in solution. The most stable conformers of the homochiral peptides adopted the interstrand hydrogen‐bond patterns, realized through ten‐ and thirteen‐membered rings. The common feature of the most stable conformers of the heterochiral peptides was the adoption of the turn‐like structures that feature the simultaneous intra‐ (seven‐membered) and interstrand (sixteen‐membered) hydrogen‐bonded

  合成了一系列含有同手性和杂手性Ala-Pro序列的肽，这些序列与诱导转铁的二茂铁-1,1'-二胺支架相连。通过IR，NMR和CD光谱研究了骨架手性和N端基团（Boc / Ac）对新型拟肽的构象性质的影响，并通过溶液中DFT研究证实了实验观察结果。同型手性肽最稳定的构象体采用链间氢键模式，通过十元和十三元环实现。杂手性肽最稳定构象异构体的共同特征是采用了具有同时氢键内部（七元）和链间（十六元）的轮状结构。与异手性衍生物相比，同质手性中两个N端基的交换对氢键模式的分布影响更大。含有吡啶部分作为金属配位点的同手性肽与二价金属离子形成1：1络合物，其中包括Zn2+，Cd 2 +，Cu 2+和Fe 2+。
• Bis[squaramido]ferrocenes as electrochemical sulfate receptors
  作者：Jakob D. E. Lane、William J. H. Greenwood、Victor W. Day、Katrina A. Jolliffe、Kristin Bowman-James、Louis Adriaenssens

  DOI：10.1039/d2nj03951f

  日期：——

  1,1′-Bis[squaramido]ferrocenes (FcSq2) are introduced as electrochemically active scaffolds for sulfate recognition. FcSq2 display high sulfate-binding affinity and selectivity in aqueous DMSO mixtures. Among tested anions, sulfate elicits a unique electrochemical response in FcSq2, enabling selective detection.

  1,1'-双[方酰胺] 二茂铁 (FcSq 2 ) 被引入作为用于硫酸盐识别的电化学活性支架。FcSq 2在含水 DMSO 混合物中显示出高硫酸盐结合亲和力和选择性。在测试的阴离子中，硫酸盐会在 FcSq 2中引发独特的电化学响应，从而实现选择性检测。
• Aminoferrocene-Based Prodrugs and Their Effects on Human Normal and Cancer Cells as Well as Bacterial Cells
  作者：Paul Marzenell、Helen Hagen、Leopold Sellner、Thorsten Zenz、Ruta Grinyte、Valeri Pavlov、Steffen Daum、Andriy Mokhir

  DOI：10.1021/jm400754c

  日期：2013.9.12

  Aminoferrocene-based prodrugs are activated under cancer-specific conditions (high concentration of reactive oxygen species, ROS) with the formation of glutathione scavengers (p-quinone methide) and ROS-generating iron complexes. Herein, we explored three structural modifications of these prodrugs in an attempt to improve their properties: (a) the attachment of a -COOH function to the ferrocene fragment leads to the improvement of water solubility and reactivity in vitro but also decreases cell-membrane permeability and biological activity, (b) the alkylation of the N-benzyl residue does not show any significant affect, and (c) the attachment of the second arylboronic acid fragment improves the toxicity (IC50) of the prodrugs toward human promyelocytic leukemia cells (HL-60) from 52 to 12 mu M. Finally, we demonstrated that the prodrugs are active against primary chronic lymphocytic leukemia (CLL) cells, with the, best compounds exhibiting an IC50 value of 1.5 mu M. The most active compounds were found to not affect mononuclear cells and representative bacterial cells.