23-Bromo-5,11,17,23-tetratert-butyl-26,27,28-tripropoxypentacyclo[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-undecaen-25-one | 648949-78-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 23-Bromo-5,11,17,23-tetratert-butyl-26,27,28-tripropoxypentacyclo[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-undecaen-25-one
• CAS: 648949-78-4
• 化学式: C₅₃H₇₃BrO₄
• 分子量: 854.064
• InChiKey: PEDUCDJJHCXIJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  16.4
• 重原子数：
  58
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  23-Bromo-5,11,17,23-tetratert-butyl-26,27,28-tripropoxypentacyclo[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-undecaen-25-one 在 palladium 10% on activated carbon 、 氢气 、 silver perchlorate 作用下， 以 乙二醇二甲醚 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 2-[(11,17,23-Tritert-butyl-28-hydroxy-25,26,27-tripropoxy-5-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)oxy]acetic acid
  参考文献：
  名称：

  Introduction of Glyco, Peptido, Carboxy, and Alkyno Substituents at the Calixarene Exo Rim via the p-Bromodienone Route

  摘要：

  The conceptually novel "p-bromodienone route", which allows the direct introduction of nucleophiles at the calixarene exo rim, has been extended to anionic C-nucleophiles (acetylides) to give chiral meta-substituted alkynocalix[4]arenes and to appropriate O-nucleophiles to obtain para-substituted glyco, peptido, and carboxy derivatives.

  DOI：

  10.1021/jo300107g
• 作为产物：
  描述：

  tris(propoxy)-4-tert-butylcalix[4]arene 在 phenyltrimethylammonium tribromide 、 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 以81%的产率得到23-Bromo-5,11,17,23-tetratert-butyl-26,27,28-tripropoxypentacyclo[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-undecaen-25-one
  参考文献：
  名称：

  该p -Bromodienone路由到杯芳烃的亲核功能化外切缘

  摘要：

  容易获得的杯芳烃对-溴代双烯酮衍生物经过银介导的亲核取代，随后用一系列不同的O-亲核体（醇和羧酸酯）进行重新麦芽糖化，以可行的产率得到对-烷氧基-或对-酰氧基杯芳烃。这种方法可以被认为是一般的“ p -bromodienone路线”功能化杯芳烃外与亲核边缘。

  DOI：

  10.1021/ol8027708

文献信息

• Exploiting the <i>p</i>-Bromodienone Route for the Formation and Trapping of Calixarene Oxenium Cations with Enamine Nucleophiles
  作者：Annunziata Soriente、Margherita De Rosa、Pellegrino La Manna、Carmen Talotta、Carmine Gaeta、Aldo Spinella、Placido Neri

  DOI：10.1021/acs.joc.8b00431

  日期：2018.6.1

  p-bromodienone derivatives can act as precursors for the formation of oxenium cations, which can be trapped with enamine C-nucleophiles. When calixarene p-bromodienones were treated with enamines, in the presence of AgClO4, the lower rim-substituted C–O–C products were obtained by an electrophilic attack of the intermediate calixarene-oxenium cation with a contemporary cone-to-partial-cone inversion of the

  这项研究表明，杯芳烃对-溴代双烯酮衍生物可以作为形成氧阳离子的前体，而氧阳离子可以被烯胺C-亲核试剂捕获。当烯胺处理杯芳烃对溴二烯酮时，在存在AgClO 4的情况下，通过中间的杯芳烃-ox阳离子与现代的锥-部分-芳族化合物的亲电子攻击获得了较低边缘取代的C–O–C产物。所涉及的芳环的圆锥反转。
• Appending aromatic moieties at the para- and meta-position of calixarene phenol rings via p-bromodienone route
  作者：Francesco Troisi、Teresa Pierro、Carmine Gaeta、Michele Carratù、Placido Neri

  DOI：10.1016/j.tetlet.2009.05.032

  日期：2009.8

  derivatives (the ‘p-bromodienone route’) with activated aromatic substrates allows the introduction of aromatic moieties at the para- or meta-position of calixarene aromatic rings. Less reactive substrates mainly afford C–O para-coupled derivatives, while more activated ones mainly give inherently chiral, C–C meta-coupled products through a dienone–phenol rearrangement of the intermediate dienone derivative

  用活化的芳族底物在杯芳烃对-溴代双烯酮衍生物（“对-溴代双烯酮途径”）上的银介导的亲核取代允许在杯芳烃芳环的对位或间位引入芳族部分。反应性较低的底物主要提供C-O对偶衍生物，而活化程度更高的底物主要通过中间二烯酮衍生物的二烯酮-苯酚重排产生内在的手性C-C间偶联产物。还观察到了杯内芳烃氧原子处的C-C对偶和O-C偶合的例子。
• Absolute Configuration Assignment of Inherently Chiral Calix[4]arenes using DFT Calculations of Chiroptical Properties
  作者：Carmen Talotta、Carmine Gaeta、Francesco Troisi、Guglielmo Monaco、Riccardo Zanasi、Giuseppe Mazzeo、Carlo Rosini、Placido Neri

  DOI：10.1021/ol101098x

  日期：2010.7.2

  The racemate of an inherently chiral meta-substituted calix[4]arene derivative 3 has been resolved via enantioselective HPLC. Measured optical rotation dispersion and electronic circular dichroism have been compared with DFT theoretical predictions. The comparison indicates that the absolute configuration of the dextrorotatory enantiomer (+)-3 is cS. The procedure has been successfully tested against

  固有手性的间位取代的杯[4]芳烃衍生物3的外消旋物已通过对映选择性HPLC拆分。已将测得的旋光色散和电子圆二色性与DFT理论预测进行了比较。比较表明，右旋对映异构体（+）- 3的绝对构型为cS。该程序已针对证实该方法有效性的文献先例进行了成功测试。
• Synthesis of the first examples of p-bromodienone and transannular spirodienone calixarene derivatives
  作者：Carmine Gaeta、Marco Martino、Placido Neri

  DOI：10.1016/j.tetlet.2003.10.035

  日期：2003.12

  The first examples of p-bromodienone calixarene derivatives (6–7 and 9–10) have been obtained by treatment of 1,5-dihydroxy-hexaalkoxycalix[8]arenes 5 or tripropoxycalix[4]arene 8 with trimethylphenylammonium tribromide and a saturated solution of NaHCO3. The first transannular spirodienone derivative 11 was only obtained in the presence of NaOH or using the KOH/I2/PEG-200 oxidizing system.

  对-溴二烯酮杯芳烃衍生物（6 – 7和9 – 10）的第一个例子是通过用三甲基苯三铵和饱和溶液处理1,5-二羟基-六烷氧基杯[8]芳烃5或三丙杯[4]芳烃8获得的。的NaHCO 3。仅在NaOH存在下或使用KOH / I 2 / PEG-200氧化系统获得第一跨环螺二烯酮衍生物11。
• Electrochemistry and ion-sensing properties of calix[4]arene derivatives
  作者：Shanshan Chen、Richard D. Webster、Carmen Talotta、Francesco Troisi、Carmine Gaeta、Placido Neri

  DOI：10.1016/j.electacta.2010.06.076

  日期：2010.9

  The cyclic voltammetric properties of several substituted calix[4]arenes were examined in acetonitrile and dichloromethane. The compounds that contained one phenolic group in the macrocyclic cavity were able to be electrochemically oxidised at positive potentials. In acetonitrile, cyclic voltammetry experiments indicated that the phenolic compounds were oxidised in a two-electron (one-proton) process over all measured scan rates (up to 50 Vs(-1)), while in dichloromethane, the oxidation process occurred by one-electron at scan rates >= 5 V s(-1), to most likely form the radical cations. In both solvents, longer timescale (minutes to hours) controlled potential coulometry experiments indicated that the oxidation process occurred by two-electrons per molecule, to form reactive diamagnetic cations that could not be reduced back to the starting materials under electrolysis conditions. The ion-sensing properties of the compounds were investigated in polymer membrane ion-selective electrodes and it was found that they responded reversibly in a Nernstian fashion to Groups 1 and 2 metals and had the highest selectivity to the cesium cation. (C) 2010 Elsevier Ltd. All rights reserved.