4-Styrylbenzyl bromide | 312767-06-9

• 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: 4-Styrylbenzyl bromide
• 英文别名: 1-(Bromomethyl)-4-(4-ethenylphenyl)benzene
• CAS: 312767-06-9
• 化学式: C₁₅H₁₃Br
• 分子量: 273.172
• InChiKey: QIFOTQYIDKVSRF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  4-Styrylbenzyl bromide 、 2,2'-Bis-triisopropylsilanyloxy-[1,1']binaphthalenyl-6,6'-diol 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.17h， 以43%的产率得到[6-[[4-(4-Ethenylphenyl)phenyl]methoxy]-1-[6-[[4-(4-ethenylphenyl)phenyl]methoxy]-2-tri(propan-2-yl)silyloxynaphthalen-1-yl]naphthalen-2-yl]oxy-tri(propan-2-yl)silane
  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
• 作为产物：
  描述：

  4-乙烯基苯硼酸 在 四(三苯基膦)钯 三溴化磷 、 sodium carbonate 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 18.0h， 生成 4-Styrylbenzyl 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