1'-((tert-butoxycarbonyl)amino)ferrocene-1-carboxylic acid | 219718-13-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 1'-((tert-butoxycarbonyl)amino)ferrocene-1-carboxylic acid
• 英文别名: 1'-(tert-butylcarbonylamino)ferrocene-1-carboxylic acid；1'-(tert-butoxycarbonilamino)ferrocene-1-carboxylic acid；1'-(tert-butxycarbonylamino)ferrocene-1-carboxylic acid；1'-(tert-butyloxycarbonylamino)ferrocene-1-carboxylic acid；[ferrocene-1-CO2H-1'-NHC(O)OC(CH3)3]；tert-butyl N-cyclopenta-2,4-dien-1-ylcarbamate;cyclopenta-2,4-diene-1-carboxylic acid;iron(2+)
• CAS: 219718-13-5
• 化学式: C₁₆H₁₉FeNO₄
• 分子量: 345.178
• InChiKey: RWSSQQLQASRSQX-UHFFFAOYSA-N

物化性质

• 熔点：
  167-168 °C

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'-((tert-butoxycarbonyl)amino)ferrocene-1-carboxylic acid 、 盐酸甲胺 在 NEt₃ 作用下， 以 四氢呋喃 为溶剂， 以23%的产率得到N-cyclopenta-2,4-dien-1-ylacetamide;iron(2+);N-methylcyclopenta-2,4-diene-1-carboxamide
  参考文献：
  名称：

  An Amide-Linked Ferrocene Dimer, [(CH₃CONHC₅H₄)Fe(C₅H₄CONHC₅H₄)Fe(C₅H₄CONHCH₃)]. Formation of Inter- and Intramolecular NH···OC Hydrogen Bonds

  摘要：

  An amide-linked ferrocene dimer, [(CH3CONHC5H4)Fe(C5H4CONHC5H4)Fe(C5H4CONHCH3)] (7), and a monomer, [(CH3CONHC5H4)Fe(C5H4CONHCH3)] (5), were synthesized, and their unique structures were determined by X-ray analysis. Amide planes are stacked with respect to each other in both crystal and dilute solution. These complexes form intermolecular NH ... O=C hydrogen bonds in the crystal. On the other hand, they form intramolecular NH ... O=C hydrogen bonds in a dilute solution as established by IR and H-1 NMR measurements. Spectral data suggest the presence of flapping structures in solution. Crystal data for 5: triclinic, P (1) over bar, a = 9.358(3) Angstrom, b = 9.947(4) Angstrom, c = 7.946(3) Angstrom, alpha = 106.86(3)degrees, beta = 113.15(3)degrees, gamma = 76.59(3)degrees, V= 644.9(5) Angstrom(3), Z = 2.7(.1)/2EtCN: orthorhombic, Pna(1), a = 7.467(4) Angstrom, b = 14.048(4) Angstrom, c = 23.400(5) Angstrom, Z = 4.

  DOI：

  10.1021/ic9806939
• 作为产物：
  描述：

  tert-butyl 1′-methoxycarbonylferrocene-1-carbamate 在 水 、 sodium hydroxide 作用下， 以 甲醇 为溶剂， 生成 1'-((tert-butoxycarbonyl)amino)ferrocene-1-carboxylic acid
  参考文献：
  名称：

  1'-氨基二茂铁-1-羧酸和脯氨酸的结合物：合成、构象分析和生物学评价

  摘要：

  我们之前的研究表明，二肽 Y-Fca-Ala-OMe (III) 转变为 Y-Ala-Fca-OMe (IV)（Y = Ac，Boc；Fca = 1'-aminoferrocene-1-羧酸）显着影响它们的构象空间。新的生物偶联物 Y-Fca-Pro-OMe (1, Y = Ac; 2, Y = Boc) 和 Y-Pro-Fca-OMe (3, Y = Boc; 4, Y = Ac)研究脯氨酸（一种众所周知的转角诱导剂）对具有交换组成氨基酸序列的小有机金属肽的构象特性的影响。为此，肽 1-4 在溶液中进行了详细的光谱分析（IR、NMR、CD 光谱）。测定了固态中肽 3 的构象。此外，

  DOI：

  10.3390/molecules190812852

文献信息

• Bis- and Trisamides Derived From 1′-Aminoferrocene-1-carboxylic Acid and α-Amino Acids: Synthesis and Conformational Analysis
  作者：Mojca Čakić Semenčić、Daniel Siebler、Katja Heinze、Vladimir Rapić

  DOI：10.1021/om801163s

  日期：2009.4.13

  and N-Boc-protected 1′-aminoferrocene-1-carboxylic acids (Boc = tert-butoxycarbonyl). The conformational preference in the solid state of selected examples was elucidated by X-ray crystallography. The chiroptical properties of chiral bis- and trisamides were investigated by circular dichroism (CD) spectroscopy in solution. The conformational preference was studied by NMR and IR spectroscopy, as well

  通过N-乙酰基和N- Boc-的溶液相肽合成，制备了带有一个或两个基于α-氨基酸（Gly，1- Ala，1- Val）的非手性和手性臂的二茂铁衍生物。保护的1'-氨基二茂铁-1-羧酸（Boc =叔-丁氧基羰基）。通过X射线晶体学阐明了所选实施例在固态中的构象偏好。通过溶液中的圆二色性（CD）光谱研究了手性双酰胺和三酰胺的手性。通过NMR和IR光谱以及分子模型（DFT）研究了构象偏好。对于双酰胺，在溶液中观察到构象文库。增加氨基酸侧链的空间体积不利于双酰胺的几种能量可及的构象异构体，并且可以通过改变环境（溶剂的类型；固体/溶液）来选择特定的构象异构体。对于三酰胺，无论保护基团的大小如何，单个构象物都可通过两个分子内氢键高度稳定，
• Conformational Switching of Multi-Responsive Ferrocenyl-Phenol Conjugates
  作者：Andreas Neidlinger、Christoph Förster、Katja Heinze

  DOI：10.1002/ejoc.201600774

  日期：2016.10

  Multifunctional conformational switches based on the ferrocenyl-salicylic acid amide motif with increasing additional complexity at the Fc moiety (R = COOMe, CONHEt, CONHFc; H-2–H-4; Fc = ferrocenyl) have been prepared and their preferred secondary structures in solution have been elucidated by NMR and IR spectroscopy in combination with conformational searches based on DFT calculations. Their distinct

  基于二茂铁基-水杨酸酰胺基序的多功能构象开关在 Fc 部分（R = COOMe、CONHEt、CONHFc；H-2-H-4；Fc = 二茂铁基）增加了额外的复杂性，并且它们优选的二级结构在已通过核磁共振和红外光谱结合基于 DFT 计算的构象搜索阐明了解决方案。它们对去质子化 ([2]––[4]–) 和氧化 ([H-2]+·–[H-4]+·) 的独特构象响应已通过红外、EPR 和紫外/可见光谱揭示为以及通过 DFT 计算。去质子化反转所有酰胺单元（双酰胺扭曲），而氧化选择性地翻转末端酰胺单元（单酰胺扭曲）。还探索了去质子化和氧化的联合作用。
• The first oligopeptide derivative of 1′-aminoferrocene-1-carboxylic acid shows helical chirality with antiparallel strands
  作者：Lidija Barišić、Maja Dropučić、Vladimir Rapić、Hans Pritzkow、Srećko I. Kirin、Nils Metzler-Nolte

  DOI：10.1039/b407771g

  日期：——

  The unnatural organometallic amino acid 1′-aminoferrocene-1-carboxylic acid (Fca) induces a turn structure in a tetrapeptide with anti-parallel strands which is stabilized by two intra-molecular hydrogen bonds in the solid state and in solution.

  不天然的有机金属氨基酸1′-氨基铁氟烷酸（Fca）在一种具有抗平行链的四肽中诱导形成转角结构，该结构在固态和溶液中通过两个分子内氢键得到稳定。
• Application of the Curtius rearrangement to the synthesis of 1′-aminoferrocene-1-carboxylic acid derivatives
  作者：William Erb、Gael Levanen、Thierry Roisnel、Vincent Dorcet

  DOI：10.1039/c7nj05020h

  日期：——

  The shortest synthesis of N-protected 1′-aminoferrocene-1-carboxylic acid from readily available ferrocene-1,1′-dicarboxylic acid is reported. 1′-Azidocarbonylferrocene-1-carboxylic acid was first obtained by reaction of the latter with diphenylphosphoryl azide. It was then converted into four amino acids by a Curtius rearrangement conducted in the presence of tert-butanol, benzyl alcohol, 9-fluorenemethanol

  据报道，由容易获得的二茂铁-1,1'-二羧酸可最短地合成N-保护的1'-氨基二茂铁-1-羧酸。首先通过使后者与二苯基磷酰基叠氮化物反应来获得1'-叠氮基羰基二茂铁-1-羧酸。然后通过在叔酸存在下进行的库尔修斯重排将其转化为四个氨基酸-丁醇，苯甲醇，9-芴甲醇或烯丙醇。氨基甲酸苄基酯和烯丙基烯丙基酯是首次报道和表征。还制备了四种相应的新琥珀酰亚胺基活化的酯，并在肽偶联中证明了它们的有用性。通过X射线晶体学阐明了各种结构，包括1'-叠氮基羰基二茂铁-1-羧酸和1,1'-二叠氮基羰基二茂铁。
• Conformational Analysis of β‐Lactam‐Containing Ferrocene Peptides
  作者：Veronika Kovač、Katarina Radolović、Ivan Habuš、Daniel Siebler、Katja Heinze、Vladimir Rapić

  DOI：10.1002/ejic.200800913

  日期：2009.1

  -disubstituted “ tetrapeptide” Fn(CO-Ala-Alm)2 (14) was prepared by reaction of ferrocene chloride 11 with 9 (Fn = 1, 1’ -ferrocenediyl). Spectroscopic and theoretical analyses revealed that compounds 12, 13, and 14 are stabilized in solution by medium strong intramolecular hydrogen bonds. In all dominant conformations (DFT calculations) intrachain bonds spanning COFc and NHAlm are present (gama-turns)

  同手性 3-氨基-1-(4-甲氧基苯基)-4-苯基-β-内酰胺 (≡ Alm) 与 Boc-Ala 共轭，在 Boc 脱保护后得到 Ala-Alm (9)（Boc = 叔丁氧基羰基，Ala = 丙氨酸）。FcCOOH (1) 和 Boc-Fca (10) 与“二肽” 9 的偶联导致分别形成 FcCO-Ala-Alm (12) 和三酰胺 Boc-Fca-Ala-Alm (13)（Fc = 二茂铁, Fca = 1'-氨基二茂铁-1-羧酸）。反应通过HOBt/EDC程序完成并且以良好的产率获得产物(HOBt = 1-羟基苯并三唑，EDC = N-(3-二甲氨基丙基)-N'-乙基碳二亚胺盐酸盐)。通过二茂铁氯化物11与9 (Fn = 1, 1' -二茂铁)的反应制备对称的1, 1'-二取代的“四肽”Fn(CO-Ala-Alm) 2 (14)。光谱和理论分析表明，化合物 12、13、和 14 在溶