1,1'-[(dimethylamino)carbonyl]ferrocene

• 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: 1,1'-[(dimethylamino)carbonyl]ferrocene
• 英文别名: 1,1'-bis(N,N-dimethylcarbamyl)ferrocene
• 化学式: C₁₆H₂₀FeN₂O₂
• 分子量: 328.194
• InChiKey: ZLXPXUGQMOAJRN-UHFFFAOYSA-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'-[(dimethylamino)carbonyl]ferrocene 、 联硼酸频那醇酯 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 C₅₄H₅₈BN₃Si 作用下， 以 四氢呋喃 为溶剂， 以78%的产率得到C₄₀H₆₄B₄FeN₂O₁₀
  参考文献：
  名称：

  手性二齿硼基配体启用的铱催化对映选择性双 C-H 硼化二茂铁：反应发展和机理见解

  摘要：

  具有平面手性的二茂铁是一类重要的特权支架，可用于多种手性配体和有机催化剂。在温和的反应条件下开发高效的催化不对称方法是该领域长期追求的目标。尽管在过去十年中记录了许多过渡金属催化的不对称 C-H 活化方法，但其中大多数与 C-C 键形成反应有关。由于 C-B 键的有用属性，我们在此报告了二茂铁的酰胺定向铱催化的对映选择性双 C-H 硼基化。这种转化成功的关键在于手性双齿硼基配体和导向基团的明智选择。目前的反应可以容忍大量的功能，提供多种手性硼化二茂铁，具有良好的对映选择性（35 个实例，对映体过量高达 98%）。我们还通过制备规模的反应和硼化产物的转化证明了合成效用。最后，根据观察到的实验数据，我们进行了 DFT 计算以了解其反应途径和手性诱导，这表明甲基 C(sp3 )-H 硼化对于通过由过渡态中相互作用的 B-O 片段引起的放大空间效应赋予高对映选择性至关重要。

  DOI：

  10.1021/acscatal.1c05299
• 作为产物：
  描述：

  1,1'-ferrocenyldicarbonyl chloride 、 二甲胺 在 三乙胺 作用下， 生成 1,1'-[(dimethylamino)carbonyl]ferrocene
  参考文献：
  名称：

  茂金属双（氮杂-冠醚）配体和相关化合物。它们的合成，配位化学和电化学性质

  摘要：

  茂金属氧化还原中心与aza-15-crown-5（1,4,7,10-tetraoxa-13）之间含有酰胺键的新的二茂铁和钌茂金属双（氮杂-皇冠醚）（11）-（14）的合成描述了-azacyclopentadecane）和aza-18-crown-6（1,4,7,10,13-pentaoxa-16-azacyclo-octadecane）。对这些化合物进行的13 C nmr变温研究揭示了一个常见的分子内动力学过程，该过程涉及绕N–CO键旋转，其旋转能量垒为阳离子（Na +或Li +）依赖。钠阳离子与二茂铁双（氮杂-冠醚）形成1：2化学计量的配合物，而钾与前者形成1：1的分子内夹心复合物，而与后者形成1：2的分子内夹心复合物。电化学研究表明，在各自的氮杂-冠醚配位位点，Na +和K +客体阳离子的结合导致二茂铁氧化波向更多的正电势转移。锂对这两种化合物产生类似的电化学作用，但是13C nmr结

  DOI：

  10.1039/dt9900003289

文献信息

• Chiral Bidentate Boryl Ligand-Enabled Iridium-Catalyzed Enantioselective Dual C–H Borylation of Ferrocenes: Reaction Development and Mechanistic Insights
  作者：Xiaoliang Zou、Yinwu Li、Zhuofeng Ke、Senmiao Xu

  DOI：10.1021/acscatal.1c05299

  日期：2022.2.4

  amide-directed iridium-catalyzed enantioselective dual C–H borylation of ferrocenes. The key to the success of this transformation relies on a chiral bidentate boryl ligand and a judicious choice of a directing group. The current reaction could tolerate a vast array of functionalities, affording a variety of chiral borylated ferrocenes with good to excellent enantioselectivities (35 examples, up to 98%

  具有平面手性的二茂铁是一类重要的特权支架，可用于多种手性配体和有机催化剂。在温和的反应条件下开发高效的催化不对称方法是该领域长期追求的目标。尽管在过去十年中记录了许多过渡金属催化的不对称 C-H 活化方法，但其中大多数与 C-C 键形成反应有关。由于 C-B 键的有用属性，我们在此报告了二茂铁的酰胺定向铱催化的对映选择性双 C-H 硼基化。这种转化成功的关键在于手性双齿硼基配体和导向基团的明智选择。目前的反应可以容忍大量的功能，提供多种手性硼化二茂铁，具有良好的对映选择性（35 个实例，对映体过量高达 98%）。我们还通过制备规模的反应和硼化产物的转化证明了合成效用。最后，根据观察到的实验数据，我们进行了 DFT 计算以了解其反应途径和手性诱导，这表明甲基 C(sp3 )-H 硼化对于通过由过渡态中相互作用的 B-O 片段引起的放大空间效应赋予高对映选择性至关重要。
• Ferrocenyl iron as a donor group for complexed silver in ferrocenyldimethyl[2.2]cryptand: a redox-switched receptor effective in water
  作者：Julio C. Medina、Timothy T. Goodnow、Maria T. Rojas、Jerry L. Atwood、Bert C. Lynn、Angel E. Kaifer、George W. Gokel

  DOI：10.1021/ja00052a064

  日期：1992.12

  Three novel ferrocene-crown derivatives have been prepared along with their previously known amide precursors. The new compounds include 1,1'-(1,4,10,13-tetraoxa-7,16-diazacyclooctadecane-7,16-dimethyl)ferrocene (2), N,N'-bis(ferrocenylmethyl)diaza-18-crown-6 (4), mp 114-116-degrees-C, and bis[N,N'-bis(cyclopentadienidylmethyl)-4,13-diaza-18-crown-6]diiron (6), mp 104-106-degrees-C. Solid-state structures have been obtained for 2.H2O (mp 101-104-degrees-C) and for the Na+ClO4- (mp 208-215-degrees-C dec) and Ag+ClO4- (MP 209-210-degrees-C dec) complexes of 2. Comparison of these structures shows that the iron atom of ferrocene is a donor ligand for Ag+ but not Na+ (the Fe-Ag+ distance is almost-equal-to 1 angstrom shorter than for Fe-Na+). Stability constants have been obtained in either CH3OH or CH3CN with Li+, Na+, K+, Ca2+, and Ag+ cations. Complexation properties for these compounds have also been assessed by use of fast atom bombardment mass spectrometry. This technique reveals interactions that were not apparent when other analytical methods were applied to these compounds. When the system was studied by electrochemical methods, a new redox couple at more positive potential was observed in the presence of certain alkali, alkaline earth, and transition metal cations. Evidence is presented that cation binding by 2 involves coordination of the cation within the cryptand cavity in contrast to related amides such as 1. Thus alkali metal redox switching, previously unknown in ferrocenyl amides, is apparent. Evidence is presented for the first example of redox switching of silver ion binding. Determination of the stability constant for the complexation of 2 with the metal cations studied shows a direct correlation with the cyclic voltammetry. The large Ag+ binding constant and electrochemistry both confirm a direct, stabilizing Ag-Fe interaction. This interaction, previously unknown for kinetically dynamic systems, is confirmed by both H-1 NMR and UV-visible spectroscopy. Na-23 NMR studies of compound 2 in the presence of Na+ show two peaks in the NMR spectrum, corresponding to free and bound Na+. This behavior is usually associated with cryptands having oxygen donors and suggests that even sodium ions, when bound, are largely encapsulated by compound 2. This strong interaction permits the first observation of redox switching involving Ag+ in aqueous solution.
• Anti-Metallocene Antibodies: A New Approach to Enantioselective Catalysis of the Diels-Alder Reaction
  作者：Jari T. Yli-Kauhaluoma、Jon A. Ashley、Chih-Hung Lo、Lee Tucker、Mary M. Wolfe、Kim D. Janda

  DOI：10.1021/ja00132a001

  日期：1995.7

  We have shown how a constrained bicyclo[2.2.2]octene hapten can elicit antibody catalysts for the Diels-Alder reaction between 4-carboxybenzyl trans-1,3-butadiene-1-carbamate and N,N-dimethylacrylamide (Gouverneur, V. E,; de Pascual-Teresa, B.; Beno, B.; Janda, K. D.; Lerner, R. A. Science 1993, 262, 204). In the present study we have developed a new approach to hapten design for elicitation of Diels-Alder catalytic antibodies. Our strategy was to engage the freely rotating eta(5)-cyclopentadienyl iron complex as the haptenic group. By applying such a flexible hapten we set out to determine if the immune system could freeze out a conformer which mimics the Diels-Alder transition state and hence produce new Diels-Alderases. If so, how would the catalytic rates, diastereo- and enantioselectivity of these antibodies compare with those of antibodies elicited by the former methodology? We generated antibodies that catalyzed the Diels-Alder reaction with high enantio- and diastereoselectivity and had effective molarities (EM) comparable to those of antibodies elicited using the constrained bicyclo[2.2.2]octene haptens. This methodology offers a new approach to the production of antibodies for the catalysis of other reactions with pericyclic, highly-ordered transition states.
• Lithium redox-responsive ferrocene bis-tertiary amide derivatives
  作者：Paul D. Beer、Harrison Sikanyika、Christopher Blackburn、Jerome F. McAleer

  DOI：10.1016/0022-328x(88)80384-x

  日期：1988.8
• Fluxonial cryptands containing metallocene units
  作者：Phillip J. Hammond、Paul D. Beer、Clare Dudman、Ian P. Danks、C.Dennis Hall、John Knychala、Martin C. Grossel

  DOI：10.1016/s0022-328x(00)98998-8

  日期：1986.6