Mono[(2-pyridylmethyl)oxy]calix[4]arene | 123207-96-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: Mono[(2-pyridylmethyl)oxy]calix[4]arene
• 英文别名: 5,11,17,23-tetra-tert-butyl-25-[(2-pyridylmethyl)oxy]-26,27,28-trihydroxycalix[4]arene；5,11,17,23-Tetratert-butyl-28-(pyridin-2-ylmethoxy)pentacyclo[19.3.1.13,7.19,13.115,19]octacosa-1(24),3,5,7(28),9,11,13(27),15(26),16,18,21(25),22-dodecaene-25,26,27-triol
• CAS: 123207-96-5；150199-08-9
• 化学式: C₅₀H₆₁NO₄
• 分子量: 740.039
• InChiKey: ZRJGUDYNUISMRN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.7
• 重原子数：
  55
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  82.8
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Mono[(2-pyridylmethyl)oxy]calix[4]arene 在 barium dihydroxide 、 potassium carbonate 、 barium(II) oxide 作用下， 以 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 33.5h， 生成 5,11,17,23-tetra-tert-butyl-25-hydroxy-26-(benzyloxy)-27-propoxy-28-(2-pyridylmethoxy)calix<4>arene
  参考文献：
  名称：

  Syntheses and optical resolution of calix[4]arenes with molecular asymmetry. Systematic classification of all possible chiral isomers derivable from calix[4]arene

  摘要：

  All possible chiral isomers that can be derived from calix[4]arene by modification of the OH groups were systematically classified. Molecular asymmetry can be generated not only by different substituents but also by conformational isomerism. The numbers of chiral isomers are 24 for tetra-O-substituted calix[4]arenes, 10 for tri-O-substituted calix[4]arenes, 3 for di-O-substituted calix[4]arenes, and 0 for mono-O-substituted calix[4]arenes. This implies that calix[4]arene is a useful building block for the design of novel asymmetric ring structures. In order to demonstrate asymmetry in these chiral calix[4]arenes, we synthesized several tetra-, tri-, and di-O-substituted calix[4]arenes by using the metal template method, the stepwise synthesis method, the protection-deprotection method, etc., which were developed in efforts directed toward regioselective O-alkylation and control of conformational isomerism in calix[4]arenes. Finally, we succeeded in complete optical resolution of chiral calix[4]arenes by an HPLC method using a chiral-packed column or by the formation of diastereomers with the (-)-menthoxyacetyl group. This article thus contains all of the molecular design concepts, syntheses, and optical resolutions of chiral calix[4]arenes.

  DOI：

  10.1021/ja00063a020
• 作为产物：
  描述：

  5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 、 2-氯甲基吡啶盐酸盐 在 sodium hydride 作用下， 以 甲苯 为溶剂， 生成 Mono[(2-pyridylmethyl)oxy]calix[4]arene
  参考文献：
  名称：

  固有手性单烷基化对叔丁基-（1,2）-杯[4]冠醚的合成，光学拆分和络合特性。

  摘要：

  单-O-烷基化的杯[4]芳烃2与三至五乙二醇二甲苯磺酸酯和K（2）CO（3）的反应提供不对称的（1,2）-杯[4]冠醚衍生物3为主要产物，以及少量的杯[4]芳烃二聚体4和混合的顺式二邻烷基二芳烷基杯[4]芳烃5。提出了形成3-5的反应机理，以及这些产物的NMR光谱特征简要讨论。通过与对映体纯的烷基铵盐的非对映异构体相互作用提供了3的手性的证据。外消旋物3的对映体拆分是通过手性固定相通过直接HPLC分离实现的。从水到CH（2）Cl（2）中的萃取研究筛选了吡啶-（1,2）-杯[4]冠醚3a-c的络合能力，结果显示碱，碱土，和重金属苦味酸盐，而对Ag（+）的提取率最高可达25％。在THF中用苦味酸银对3a-c进行的UV和pH值测量表明形成了1：1：1（金属：配体：苦味酸）物种，log K在3.1-3.7范围内。

  DOI：

  10.1021/jo970934e

文献信息

• Inherently chiral calix[4]crown ethers
  作者：Sebatiano Pappalardo、Melchiorre F. Parisi

  DOI：10.1016/0040-4039(96)00047-0

  日期：1996.2

  The first inherently chiral calix[4]crown ethers 2 have been obtained by the base-catalysed reaction of mono-alkylated p-tert-butylcalix[4]arenes 1 with oligoethylene glycol ditosylates. Preliminary 1H NMR studies suggest the ability of these receptors to bind either chiral alkylammonium or Zn2+ guest species within the hydrophilic pocket generated by the O-alkyl residues at the lower rim.

  第一固有手性杯[4]冠醚2是通过单烷基化对叔丁基杯[4 ]芳烃1与低聚乙二醇二甲苯磺酸酯的碱催化反应而获得的。初步的1 H NMR研究表明，这些受体具有结合下边缘的O-烷基残基所产生的亲水性口袋中的手性烷基铵或Zn 2+客体的能力。
• Synthesis and Optical Resolution of a Chiral Calix[4]arene Asymmetrically-Substituted on the Lower Rim
  作者：Koji Iwamoto、Akihiro Yanagi、Takashi Arimura、Tsutomu Matsuda、Seiji Shinkai

  DOI：10.1246/cl.1990.1901

  日期：1990.10

  A cone-shaped, asymmetrically-substituted calix[4]arene has been synthesized by a stepwise O-alkylation method and optically-resolved by an HPLC method. This is the first example for successful optical resolution of a calix[4]arene with ring-originating chirality.

  锥形、不对称取代的杯[4]芳烃通过逐步O-烷基化方法合成，并通过HPLC方法进行光学解析。这是成功光学拆分具有环源手性的杯[4]芳烃的第一个例子。
• Synthetic strategies to inherently chiral calix[4]arenes with mixed ligating functionalities at the lower rim
  作者：George Ferguson、John F. Gallagher、Luigi Giunta、Placido Neri、Sebastiano Pappalardo、Melchiorre Parisi

  DOI：10.1021/jo00080a010

  日期：1994.1

  The syntheses of 19 atropisomeric inherently chiral calix[4]arenes derived from syn-proximal (1,2)-bis[(2-pyridylmethyl)oxy]calix[4]arene 2 and mixed syn-distal (1,3)-[(2-pyridylmethyl)oxy][(2-quinolylmethyl)oxy]calix[4] arene 6 are described. Treatment of 2 with 1 equiv of electrophile RX in DMF in the presence of Cs2CO3 afforded racemic tri-O-alkylated cone conformers 3a-k (A(alpha)A(alpha)B(alpha)C(alpha) type), while with an excess of alkylating agent under analogous conditions the chiral tetra-O-alkylated partial cone conformers 4a-d (A(alpha)A(alpha)B(alpha)B(beta) type) were formed. Similarly, exhaustive alkylation of 6 with either PicCl.HCl or QuinCl.HCl gave the chiral partial cone derivatives 7a,b (A(alpha)A(alpha)A(beta)B(alpha) type), respectively. Further alkylation of 3i (R=benzyl) with PicCl.HCl and Cs2CO3 provided partial cone derivative 7c (A(alpha)A(alpha)A(beta)B(alpha) type), while with PrBr and NaH cone tetraether 8 (A(alpha)A(alpha)B(alpha)C(alpha) type) was obtained. Proton and carbon NMR spectral features of these compounds are discussed. Atropisomerism in tri-O-alkylated calix[U arenes was demonstrated by dynamic NMR studies on the less encumbered allyl derivative 3a, which showed no hint for conformational inversion up to 375 K. 2D COSY spectra clearly show that in partial cone structures 4d and 7a-c the N-heteroaryl pendant group of the rotated aryl moiety lies in, and effectively fills, the calix cavity produced by the remaining three aryl rings, The structure of the trisubstituted racemic calix[4]arene 3i has been determined by X-ray crystallography. The molecule adopts a distorted cone conformation with the two pendant pyridinyl groups in the syn-proximal arrangement on one side of the pendant benzyl moiety. There is an intramolecular O-H...O hydrogen bond between the phenolic oxygen OD and the proximal ethereal oxygen OA (to which is bonded the benzyl residue) with O...O 2.85 Angstrom.
• Calix[4]arenes with pyridine pendant groups. Regioselective proximal alkylation at the "lower rim"
  作者：Francesco Bottino、Luigi Giunta、Sebastiano Pappalardo

  DOI：10.1021/jo00284a001

  日期：1989.11
• Functionalization of calix[4]arenes by alkylation with 2-(chloromethyl)pyridine hydrochloride
  作者：Sebastiano Pappalardo、Luigi Giunta、Mario Foti、George Ferguson、John F. Gallagher、Branko Kaitner

  DOI：10.1021/jo00035a016

  日期：1992.4

  The syntheses, structures, and conformations of nine of the 13 possible [(2-pyridylmethyl)oxy]calix[4]arene conformers obtainable by direct substitution on calix[4]arenes 1a,b are described. The conformer distribution in the exhaustive O-alkylation of 1a,b with 2-(chloromethyl)pyridine hydrochloride (PicCl.HCl) in N, N,N-dimethylformamide (DMF) is strongly affected by the base applied: NaH induces only cone conformers, while K2CO3 or Cs2CO3 lead preferentially to partial cone and/or 1,3-alternate conformers, depending on the para substituent of the starting calix[4]arene. Single-crystal X-ray analyses on tetra-O-alkylated cone 1k,1 and partial cone 2c have been conducted. Molecule 1k has a distorted cone conformation with pendant OCH2Py groups; a methanol of solvation is hydrogen bonded to one pyridine N atom and is exo to the calix cavity. The crystal structure of 11 contains two independent distorted cone shaped molecules per asymmetric unit which differ principally in the relative orientations of the OCH2Py groups. In the partial cone conformer 2c the conformation adopted is such that the pendant OCH2Py group of the rotated aryl ring lies in, and effectively fills, the calix cavity produced by the remaining three aryl rings; as in 1k a methanol of solvation is hydrogen bonded to a pyridine N atom exo to the calix cavity. Regioselective syn-proximal (1,2-) or syn-distal (1,3-) difunctionalization at the lower rim of calix[4]arenes has been also achieved. Syn-1,2-disubstituted derivatives have proved to be useful intermediates for the stereoselective synthesis of tri-O-alkylated cone conformers, calix[4]arenes with mixed ligating groups in the sequence AABB at the lower rim, for inherently chiral calix[4]arenes, and for the transfer of proximal regioselectivity from the lower to the upper rim. On the basis of stepwise O-alkylation of calix[4]arenes, and with the aid of MM2 calculations on the involved intermediates and their anions, a possible genesis of the various conformers is proposed.