(2S,4S)-4-(methoxymethyl)-2-ferrocenyl-1,3-dioxane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: (2S,4S)-4-(methoxymethyl)-2-ferrocenyl-1,3-dioxane
• 英文别名: (2S,4S)-2-ferrocenyl-4-(methoxymethyl)-1,4-dioxane；(2S,4S)-2-ferrocenyl-4-(methoxymethyl)-1,3-dioxane；Kagan’s acetal；Kagan’s ferrocene acetal；(S,S)-[(C5H5)Fe(C5H4C4H6O2CH2OCH3)]；2S,4S-(C5H5)Fe(C5H4C4H6O2Ch2OCH3)
• 化学式: C₁₆H₂₀FeO₃
• 分子量: 316.18
• InChiKey: RBWYORLUWRIMDH-ULEGLUPFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.19
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,4S)-4-(methoxymethyl)-2-ferrocenyl-1,3-dioxane 在 叔丁基锂 、 对甲苯磺酰叠氮 作用下， 以 乙醚 、 四氢呋喃 为溶剂， 反应 1.5h， 生成 (2S,4S,S_p)-2-(2-azidoferrocenyl)-4-(methoxymethyl)-1,3-dioxane
  参考文献：
  名称：

  立体选择性地获得二茂铁基平面手性三唑鎓盐

  摘要：

  描述了具有二茂铁基平面手性的三唑鎓盐的首次合成。它是通过内酰胺中间体的构建从对映纯的Kagan乙缩醛中获得的。制备相应的1,2,4-三唑基亚甲基-Cu（I）配合物。通过X射线衍射分析表征其结构以及母体三唑鎓盐。

  DOI：

  10.1016/j.jorganchem.2015.07.038
• 作为产物：
  描述：

  二茂铁甲醛 生成 (2S,4S)-4-(methoxymethyl)-2-ferrocenyl-1,3-dioxane
  参考文献：
  名称：

  Synthesis and structure of planar chiral ferroceno[d]pyridazinones, the first representatives of a novel class of fused metallocenes

  摘要：

  A series of planar chiral ferroceno[d]pyridazinones was prepared by hydrazine-mediated cyclisations of (Sp)-2-formylferrocenoyl fluoride obtained in two steps from (2S,4S)-4-(methoxymethyl)-2-ferrocenyl-1,3-dioxane. Further derivatives based on the novel heterocyclic scaffold were resulted by means of the facile N-alkylation reactions carried out on the easily accessible fused product derived from the hydrazine-mediated cyclisation. Upon treatment with hydrazine (Sp)-2-formylferroce carboxylic acid, the precursor of the acid fluoride with enhanced reactivity, afforded a dimeric azine avoiding cyclisation. The spectacular difference between the experimentally observed reactivity of the bifunctional formyl-ferrocenes was disclosed by comparative DFT analysis of the assumed hydrazone-and hydrazide intermediates with different values of LUMO energy associated with different conformation. The structures of the new compounds were established by IR and NMR spectroscopy, including HMQC, HMBC and DNOE measurements. (C) 2011 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2011.01.032

文献信息

• Diastereoselective deprotonative metalation of chiral ferrocene derived acetals and esters using mixed lithium–cadmium and lithium–zinc combinations
  作者：Gandrath Dayaker、Aare Sreeshailam、D. Venkata Ramana、Floris Chevallier、Thierry Roisnel、Shinsuke Komagawa、Ryo Takita、Masanobu Uchiyama、Palakodety Radha Krishna、Florence Mongin

  DOI：10.1016/j.tet.2014.02.010

  日期：2014.3

  derivative in 74% yield with 90% de (SP diastereoisomer) using the base generated from CdCl2 and Li(TMP) (3 equiv), and in 85% yield with 91% de (SP diastereoisomer) through a double asymmetric induction using a chiral lithium–zinc base generated from ZnCl2·TMEDA and lithium (R)-bis(1-phenylethyl)amide (4 equiv). In contrast, using a combination prepared from ZnCl2 and Li(TMP) (4 equiv) with the ferrocene carboxylate

  原位双金属组合，尤其是由MCl 2（TMEDA）（M = Zn，Cd; TMEDA = N，N，N'，N'-四甲基乙二胺）和Li（TMP）（3或4当量，TMP = 2筛选了（2,6,6-四甲基哌啶子基）具有手性基团的非对映选择性去质子化二茂铁的能力。使用由CdCl 2和Li（TMP）（3当量）生成的碱，由双丙酮d-葡萄糖生成的二茂铁羧酸盐以74％的产率提供90％的de（S P非对映异构体）相应的2-碘衍生物。收率91％de（S P非对映异构体）通过使用由ZnCl 2 ·TMEDA和锂（R）-双（1-苯乙基）酰胺（4当量）生成的手性锂锌基双不对称诱导。相比之下，使用由ZnCl 2和Li（TMP）（4当量）制备的组合物与由6-（叔丁氧羰基氨基）-6-脱氧-3- O-甲基-1,2- O-异亚丙基获得的二茂铁羧酸盐-α- d -glucofuranose导致ř P分离之后碘在57％衍生物的产率。在分离的S
• Planar chiral ferrocene salen-type ligands featuring additional central and axial chirality
  作者：Heimo Wölfle、Holger Kopacka、Klaus Wurst、Karl-Hans Ongania、Hans-Helmut Görtz、Peter Preishuber-Pflügl、Benno Bildstein

  DOI：10.1016/j.jorganchem.2005.11.051

  日期：2006.3

  We report on novel chiral tridentate [NO2]H2 and tetradentate [N2O2]H2 Schiff base ligands containing a planar chiral ferrocene moiety linked to hydroxyl-imine or diimine donors with central or axial chirality. Structurally, these ligands resemble half-salen and salen systems designed for stereoselective applications of their transition metal complexes in homogeneous catalysis. The modular synthesis

  我们报道了新型手性三齿[NO 2 ] H 2和四齿[N 2 O 2 ] H 2包含平面手性二茂铁部分的席夫碱配体与具有中心或轴向手性的羟基亚胺或二亚胺供体连接。从结构上讲，这些配体类似于为它们的过渡金属配合物在均相催化中的立体选择性应用而设计的salen-salen和salen体系。模块化合成包括手性二茂铁或五甲基二茂铁乙缩醛的非对映选择性金属化，然后分别进行立体保守的羟烷基化和与手性羟胺或二胺的缩合。与Salen型系统相比，这些配体的重要优点是它们对醇盐供体位点的可调节的空间保护。总共制备了18种不同的电子和空间性质的配体，并通过NMR，IR，
• Diastereoselective Double C−H Functionalization of Chiral Ferrocenes with Heteroaromatics
  作者：Kristína Plevová、Péter Kisszékelyi、Denisa Vargová、Samuel Andrejčák、Viktor Tóth、Lukáš Fertáľ、Erik Rakovský、Juraj Filo、Radovan Šebesta

  DOI：10.1002/chem.202102624

  日期：2021.11.5

  Pd-Complexes with N-Boc protected amino acids catalyze diastereoselective oxidative double C−H functionalization of chiral ferrocenyl amines with heteroarenes. A range of thiophene, pyrrole, furan and indole ferrocene derivative can be obtained in a single step and in high diastereomeric purities. C−H activation products can be transformed to corresponding phosphines. 19F NMR and DFT calculations helped

  带有N - Boc 保护的氨基酸的Pd-配合物催化具有杂芳烃的手性二茂铁胺的非对映选择性氧化双 C-H 官能化。一系列噻吩、吡咯、呋喃和吲哚二茂铁衍生物可以在一个步骤中以高非对映体纯度获得。CH 活化产物可以转化为相应的膦。19 F NMR 和 DFT 计算有助于阐明反应机理和立体诱导的原因。
• Planar Chiral Cyclic (Amino)(ferrocenyl)carbene as Ligand for Transition Metals
  作者：Risa Yasue、Masaru Miyauchi、Kazuhiro Yoshida

  DOI：10.1002/adsc.201600999

  日期：2017.1.19

  Planar chiral ferrocene‐fused iminium salts were synthesized in enantiomerically pure form. The novel planar chiral cyclic (amino)(ferrocenyl)carbene successfully generated from such salt was subjected to carbene trapping experiments with sulfur and copper chloride. The utility of the carbene as a chiral ligand for transition metals was preliminarily demonstrated in the copper‐catalyzed enantioselective

  平面手性二茂铁融合的亚胺盐以对映体纯形式合成。由这种盐成功生成的新型平面手性环状（氨基）（二茂铁基）卡宾用硫和氯化铜进行卡宾捕集实验。卡宾用作过渡金属的手性配体的用途已在铜催化的α，β-不饱和酯的对映选择性β-硼化中得到了初步证明。
• An efficient and highly stereoselective synthesis of new P-chiral 1,5-diphosphanylferrocene ligands and their use in enantioselective hydrogenation
  作者：Weiping Chen、Stanley M. Roberts、John Whittall、Alexander Steiner

  DOI：10.1039/b601952h

  日期：——

  An efficient and highly stereoselective synthesis of P-chiral 1,5-diphosphanylferrocene ligands has been developed, and the introduction of P-chirality in ferrocene-based phosphine ligands enhances the enantioselective discrimination produced by the corresponding catalyst when matching of the planar chirality, the chirality at carbon and the chirality at phosphorus occurs.

  已开发出有效且高度立体选择性的P-手性1,5-二膦基二茂铁配体合成方法，在二茂铁基膦配体中引入P-手性可增强相应催化剂在平面手性相匹配时产生的对映选择性。出现碳的手性和磷的手性。