3,5-Di[3,5-di(4-vinylbenzyloxy)benzyloxy]benzyl bromide | 199277-79-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3,5-Di[3,5-di(4-vinylbenzyloxy)benzyloxy]benzyl bromide
• CAS: 199277-79-7
• 化学式: C₅₇H₅₁BrO₆
• 分子量: 911.932
• InChiKey: ZXJZEJNHVCWFSL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.63
• 重原子数：
  64.0
• 可旋转键数：
  23.0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  55.38
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  3-叔丁基-2,5-二羟基苯甲醛 、 3,5-Di[3,5-di(4-vinylbenzyloxy)benzyloxy]benzyl bromide 在 potassium carbonate 、 potassium iodide 作用下， 以 丙酮 为溶剂， 反应 4.0h， 以22%的产率得到5-{3,5-Bis-[3,5-bis-(4-vinyl-benzyloxy)-benzyloxy]-benzyloxy}-3-tert-butyl-2-hydroxy-benzaldehyde
  参考文献：
  名称：

  制备用于与苯乙烯交联悬浮共聚的树枝状和非树枝状苯乙烯基Salens的方法，以及在对映选择性环氧化和杂Diels-Alder反应中多次使用相应的Mn和Cr配合物。

  摘要：

  在使用TADDOL和BINOL之后，我们现在制备了带有两个至八个苯乙烯基的Salen衍生物（2、3、14、15、18、19、20、21），用于与苯乙烯交联共聚。Salen核要么衍生自（R，R）-二苯基乙二胺（3，15，19，21），要么衍生自（R，R）-环己烷二胺（2，14，18，20）。使用Suzuki（cf.1）或Sonogashira交叉偶联（cf.11）和/或用树状苯乙烯基取代的Fréchet型苄基进行酚醚化（cf.5、7）将苯乙烯基连接到水杨醛部分上分支溴化物。随后与二胺的缩合提供手性Salens。还制备了缺少外围乙烯基的相应Salens（参见12、13、16、17），用于比较均相溶液中的催化活性和聚苯乙烯中的催化活性。按照Itsuno和Fréchet的程序，苯乙烯和苯乙烯基Salens的交联自由基悬浮共聚，得到的珠子（直径约400微米）装有Mn或Cr（每克聚合物约0.2 mmo

  DOI：

  10.1002/1521-3765(20010702)7:13<2873::aid-chem2873>3.0.co;2-c
• 作为产物：
  描述：

  3,5-Di[3,5-di(4-vinylbenzyloxy)benzyloxy]benzyl alcohol 在 四溴化碳 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 49.0h， 以63%的产率得到3,5-Di[3,5-di(4-vinylbenzyloxy)benzyloxy]benzyl bromide
  参考文献：
  名称：

  Immobilization of BINOL by Cross-Linking Copolymerization of Styryl Derivatives with Styrene, and Applications in Enantioselective Ti and Al Lewis Acid Mediated Additions of Et2Zn and Me3SiCN to Aldehydes and of Diphenyl Nitrone to Enol Ethers

  摘要：

  The chiral ligand 1,1'-bi-2-naphthol (BINOL) has been succesfully immobilized on polystyrene. Several dendritic and non-dendritic BINOL derivatives (3, and 13-17), bearing at least two polymerizable styryl groups, were prepared and fully characterized. Suspension copolymerization of the MOM- or TIPS-protected cross-linking BINOL ligands (MOM = methyloxymethyl, TIPS = triisopropylsilyl) with styrene, cleavage of the protecting-groups, and loading with a Lewis-acid afforded catalytically active polystyrene-supported BINOLates. The polymer-bound BINOLs p-3, and p-13-p-16 were tested in the Ti-BINOLate-mediated addition of Et2Zn to PhCHO. The enantioselectivities (up to 93%) and conversions obtained with the polymer-bound catalysts were in most cases identical (within experimental error) to those obtained with the unsubstituted 1,1'-bi-2-naphthol and with the non-polymerized BINOL cross-linkers under homogeneous conditions. Special focus was put on the reusability of the supported catalyst: the polymer-beads were used in up to 20 consecutive catalytic runs, with the best polymers showing no or only minor loss of selectivity. BINOL-polymers p-17, obtained by copolymerization of a 3,3'-distyryl-substituted BINOL 17a with styrene, were used in the BINOL AlMe-mediated cycloaddition of diphenyl nitrone with alkyl vinyl ethers. In all cases the exolendo selectivity (greater than or equal to 92:8) and the enantioselectivities with which the exo-cycloadducts were formed (greater than or equal to 95%) correspond to those observed in the homogeneous reactions. A dendritically cross-linked BINOL-polymer was also employed in the Ti-BINOLate-mediated cyanosilylation of pivalaldehyde. The enantiopurity of the cyanohydrine obtained in the first run was as high as in the homogeneous reaction (72%); surprisingly the catalytic performance of the supported catalyst increased steadily during the first catalytic cycles to reach 83%. Thus, cross-linking BINOLs can be succesfully incorporated into a polystyrene matrix (without racemization!) to give poly mer-bound BINOL ligands that give excellent performance over many catalytic cycles with catalytic activities comparable with those of soluble analogues.

  DOI：

  10.1002/1521-3765(20001016)6:20<3692::aid-chem3692>3.0.co;2-0