p-tert-Butylcalix<4>arene triflate

• 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: p-tert-Butylcalix<4>arene triflate
• 英文别名: p-tert-butylcalix[4]arene triflate；(5,11,17,23-Tetratert-butyl-26,27,28-trihydroxy-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
• 化学式: C₄₅H₅₅F₃O₆S
• 分子量: 780.989
• InChiKey: WYBOGVGWDCTIGB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.1
• 重原子数：
  55
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  112
• 氢给体数：
  3
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  1,3-bis(triflate)-p-tert-butylcalix[4]arene 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二甲基亚砜 为溶剂， 反应 12.0h， 以49%的产率得到p-tert-Butylcalix<4>arene triflate
  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

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。
• 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
• Calix[4]arene Sulfonates: Palladium-Catalyzed Intermolecular Migration of Sulfonyl Groups and Isolation of a Calix[4]arene in a Chiral 1,2-Alternate Conformation
  作者：Juan J. Gonzalez、Pedro M. Nieto、Pilar Prados、Antonio M. Echavarren、Javier de Mendoza

  DOI：10.1021/jo00128a012

  日期：1995.11

  An intermolecular migration of sulfonyl groups in 1,3-bistriflate and 1,3-bismesylate derivatives of p-tert-butylcalix[4]arene (1) takes place in the presence of both a palladium catalyst and chloride anion. The process leads to the clean formation of 1:1 mixtures of mono- and trisubstituted derivatives that could not be prepared directly from 1 by sulfonylation reactions. A trismesylate 7b is obtained as a minor derivative under the conditions required for the mesylation of 1. Compound 7b exists in a 1,2-alternate conformation, which is chiral due to the pattern of substituents.
• 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
  作者：Shinya Tanaka、Takafumi Umetsu、Satoru Nebuya、Naoya Morohashi、Tetsutaro Hattori

  DOI：10.1021/jo502563z

  日期：2015.1.16

  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.