1,3-bis(triflate)-p-tert-butylcalix[4]arene | 172878-84-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 1,3-bis(triflate)-p-tert-butylcalix[4]arene
• 英文别名: [5,11,17,23-Tetratert-butyl-26,28-dihydroxy-27-(trifluoromethylsulfonyloxy)-25-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-dodecaenyl] trifluoromethanesulfonate
• CAS: 172878-84-1
• 化学式: C₄₆H₅₄F₆O₈S₂
• 分子量: 913.052
• InChiKey: DYNMDPYHIVWAAW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.2
• 重原子数：
  62
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  144
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  1,3-bis(triflate)-p-tert-butylcalix[4]arene 在 copper(l) iodide 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 potassium iodide 作用下， 以 甲苯 为溶剂， 反应 12.0h， 以63%的产率得到5,11,17,23-tetra-tert-butyl-26,28-diiodopentacyclo[19.3.1.1^3,7.1^9,13.1^15,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecane-25,27-diol
  参考文献：
  名称：

  1,3-Diiodocalix[4]arene: Synthesis by Ullmann-Type Iodination of 1,3-Bistriflate Ester of Calix[4]arene, Conformational Analysis, and Transformation into 1,3-Dicarboxy-, Diformyl-, and Dialkylcalix[4]arenes

  摘要：

  A facile synthesis of 1,3-diiodocalix[4]arene 6 has been achieved by copper-catalyzed iodination of the 1,3-bistriflate ester 2a of p-tert-butylcalix[4]arene. After protection of the hydroxy groups with iodomethane, diiodide 6 is subjected to halogenlithium exchange with butyllithium, followed by carbonation with CO2 or formylation with N-formylpiperidine and subsequent deprotection of the hydroxy groups to give novel dicarboxylic acid 11 or dialdehyde 16 in practical yields. The iodo groups of diiodide 6 pass through the calixarene macrocycle; the activation free energy for the conversion of the more stable syn conformer 6syn to the less stable anti conformer 6anti is Delta G(double dagger =) = 104 kJ mol(-1) at 298 K. Dialdehyde 16 shows fast self-exchange between two equivalent species with a cone conformation, Delta G(double dagger), being 63.2 kJ mol1. Dicarboxylic acid 11 adopts a cone conformation and forms a dimer in solution as suggested by 1H NMR and X-ray crystallographic analyses. The arrangement of the iodide groups of compound 6 can be fixed predominantly to anti (17a and 17b) by introducing bulky alkyl groups (e.g., propyl groups) onto the hydroxy groups. The stereospecific alkylation of the iodo groups of the resulting di-O-alkylated anti-1,3-diiodides provides access to the anti-1,3-dialkylcalixarenes 19, which is otherwise difficult to obtain.

  DOI：

  10.1021/jo502563z
• 作为产物：
  描述：

  三氟甲烷磺酰氯 、 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrahydroxycalix-4-arene 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 生成 1,3-bis(triflate)-p-tert-butylcalix[4]arene
  参考文献：
  名称：

  Synthesis of fluorocalix[4]arene and estimation of intramolecular C F⋯HO hydrogen bond

  摘要：

  A weak intramolecular C-F center dot center dot center dot HO hydrogen bond was detected in fluorocalix[4]arene 1 by using NMR and IR spectroscopies, and crystallographic analysis. This interaction was detected in several molecules; however, the molecular design must be very precise to detect the weak H.B. In this case, H.B. patterns in solution and solid states were determined and the free energy of the aromatic ring inversion was estimated by VT-NMR studies. Based on the aromatic ring inversion potentials of 1, calix[4]arene, and monodeoxycalix[4]arene, the free energy of the C-F center dot center dot center dot HO H.B. in this system was estimated. (C) 2015 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2015.11.001

文献信息

• Synthesis of Calix[4]arene Triflates and Their Unusual Chemical Reactivity in Palladium-Catalyzed Reactions
  作者：Sultan Chowdhury、John N. Bridson、Paris E. Georghiou

  DOI：10.1021/jo000003u

  日期：2000.6.1

  p-tert-butylcalix[4]arene mono-, bis-, tris-, and tetrakistriflates 3, 2, 4, and 5, respectively, and their respective reactions, under typical Pd-catalyzed carbonylative, Suzuki-Miyaura coupling, or deoxygenation conditions are described. A novel, nonsolvent-derived 1:1 clathrate (6) of benzophenone and 3 was formed from the palladium-catalyzed carbonylative reaction of phenylboronic acid and 2. The X-ray crystal

  在典型的Pd催化羰基化，Suzuki-Miyaura偶联作用下，分别形成对叔丁基杯[4]芳烃单，双，三，三和四氟三氟甲磺酸3、2、4和5，以及它们各自的反应描述了脱氧条件。钯催化苯硼酸和2的羰基化反应，制得了一种新的，非溶剂衍生的二苯甲酮1：1笼形物（6）和3。据报道有]芳烃衍生物。在Pd催化的2脱氧过程中形成了另外的1：1的三乙胺和3的包合物。
• Straightforward synthesis and catalytic applications of rigid N,O-type calixarene ligands
  作者：Varun Rawat、Konstantin Press、Israel Goldberg、Arkadi Vigalok

  DOI：10.1039/c5ob01987g

  日期：——

  Here, we report a simple one-step access to new rigid N,O-calixarene ligands which is based on copper-catalyzed amination at the lower rim. We also present the coordination properties of these ligands with some main group and transition metals leading to new complexes with superior catalytic activity, in several organic transformations, compared with calixarene metal complexes reported in the literature

  在这里，我们报告了一种简单的单步访问新的刚性N，O-杯芳烃配体的方法，该配体基于下边缘的铜催化胺化。与文献中报道的杯芳烃金属配合物相比，我们还展示了这些配体与一些主要基团和过渡金属的配位性能，这些配合物导致了具有优异催化活性的新配合物，在一些有机转化中。
• Synthesis of Mono- and 1,3-Diaminocalix[4]arenes via Ullmann-Type Amination and Amidation of 1,3-Bistriflate Esters of Calix[4]arenes
  作者：Yuka Nakamura、Shinya Tanaka、Ryuichi Serizawa、Naoya Morohashi、Tetsutaro Hattori

  DOI：10.1021/jo102566e

  日期：2011.4.1

  instead of the hydroxy group(s) at the 28-position or at both the 26- and 28-positions of p-tert-butylcalix[4]arene (1a) and p-tert-butylthiacalix[4]arene (1b), via the Ullmann-type amination or amidation. Thus, the copper-catalyzed or mediated amination of the 1,3-bistriflate ester (2a) of 1a with benzylamine affords either mono(benzylamino) triflate 7a or 1,3-bis(benzylamine) 8 in a high yield, depending

  描述了用于制备单胺4和1，3-二胺5的实用方法，所述单胺4和1，3-二胺5在28位或在26位和28位都带有一个或两个氨基而不是羟基的p -叔-butylcalix [4]芳烃（1A）和p -叔-butylthiacalix [4]芳烃（1B），通过乌尔曼型胺化或酰胺化。因此，用苄胺对1a的1，3-二rifriflate酯（2a）进行铜催化或介导的胺化反应可得到单（苄基氨基）三氟甲磺酸酯7a或1，3-双（苄基胺）8。取决于反应条件，产率高。另一方面，1b的1，3-二rifriflate酯（2b）抵抗分解并且在化学计量条件下产生三氟甲磺酸单（苄基氨基）7b。的二取代2B是通过酰胺化与甲苯磺酰胺来实现，得到1,3-双（甲苯磺酰胺）17B。7a的苄氨基部分的氢解，然后Tf部分的水解，得到单胺4a，而8的氢解得到1,3-二胺5a。7b的氨基部分可以在酸性条件下脱保护，在水解后得到单胺4b。17b的水
• Synthesis and characterization of oxygen depleted tert-amine calix[4]arene ligands and study the effect on sigma non-opioid intracellular protein receptor
  作者：Navaneet Chaturvedi、Abha Mishra、Varun Rawat

  DOI：10.1007/s11224-019-01324-x

  日期：2019.10

  distribution of the clusters suggests that scattering of the cluster’s popularity is a measure of fast structural transitions in both complexes. Current study utilizes modern approach to synthesis, characterization, and simulation of our ligands. This study appropriately highlights the effect of our ligands on SigNOR Protein, which might further be extended to potential in vitro and in vivo bioassay.

  本研究侧重于蛋白质靶标上的缺氧杯[4]芳烃配体的生物学前景。由于其广泛的医学相关性，合成了耗氧双（哌啶）（BPD）和双（吡唑）（BPZ）配体，并通过核磁共振和质谱法对其进行了表征。此外，利用分子对接和分子动力学模拟来了解配体在选择 sigma 非阿片细胞内受体 (SigNOR) 作为合适的蛋白质靶标时的行为。模拟按三个复杂程度进行：（1）Apo SigNOR，（2）BPD：SigNOR，和（3）BPZ：SigNOR。在详细分析之前，对三个复杂系统进行了稳定性检查。根据结合自由能的估计结果，两个配体具有相同的结合自由能，反过来，暗示它们的相似作用；然而，范德华和静电势等能量成分推荐 BPZ 被确定为 SigNOR 上的竞争药物。此外，集群的时间分布表明，集群流行度的分散是两个复合体中快速结构转变的衡量标准。目前的研究利用现代方法来合成、表征和模拟我们的配体。这项研究适当地强调了我们的配体对 SigNOR
• Entry to new N,O-ligands from oxygen-depleted calixarenes
  作者：Ella Tzadka (Bukhaltsev)、Israel Goldberg、Arkadi Vigalok

  DOI：10.1039/b816343j

  日期：——

  We prepared and characterized titanium complexes of a new mixed N,O-ligand obtained from oxygen-depleted calixarenes, which show interesting catalytic activity compared with complexes of a “regular” calixarene ligand.

  与 "常规 "钙钛矿配体的钛络合物相比，这种钛络合物显示出有趣的催化活性。