2'-carboxy-4-ethynyl-4''-trimethylsilylethynyl-5'-(1-octynyl)-1,1':3',1''-terphenyl | 1034710-61-6

• 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: 2'-carboxy-4-ethynyl-4''-trimethylsilylethynyl-5'-(1-octynyl)-1,1':3',1''-terphenyl
• 英文别名: 2-(4-Ethynylphenyl)-4-oct-1-ynyl-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid；2-(4-ethynylphenyl)-4-oct-1-ynyl-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid
• CAS: 1034710-61-6
• 化学式: C₃₄H₃₄O₂Si
• 分子量: 502.728
• InChiKey: RUQPTLGEHFLJCU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.25
• 重原子数：
  37
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2'-carboxy-4-ethynyl-4''-trimethylsilylethynyl-5'-(1-octynyl)-1,1':3',1''-terphenyl 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以84%的产率得到2-[4-[4-[4-[2-Carboxy-5-oct-1-ynyl-3-[4-(2-trimethylsilylethynyl)phenyl]phenyl]phenyl]buta-1,3-diynyl]phenyl]-4-oct-1-ynyl-6-[4-(2-trimethylsilylethynyl)phenyl]benzoic acid
  参考文献：
  名称：

  Sequence- and Chain-Length-Specific Complementary Double-Helix Formation

  摘要：

  The artificial sequential strands consisting of two, three, or four m-terphenyl groups joined by diacetylene linkers with complementary binding sites, either the chiral amidine (A) or achiral carboxyl (C) group, were synthesized in a stepwise manner. Using circular dichroism and H-1 NMR spectroscopies along with liquid chromatography, we showed that, when three dimeric molecular strands (AA, CC, and AC) or six trimeric molecular strands (AAA, CCC, AAC, CCA, ACA, and CAC) were mixed in solution, the complementary strands were sequence-specifically hybridized to form one-handed double-helical dimers AA center dot CC and (AC)(2) or trimers AAA center dot CCC, AAC center dot CCA, and ACA center dot CAC, respectively, through complementary amidinium-carboxylate salt bridges. Upon the addition of CCA to a mixture of AAA, AAC, and ACA, the AAC center dot CCA double helix was selectively formed and then isolated from the mixture by chromatography. Moreover, the homo-oligomer mixtures of amidine or carboxylic acid from the monomers to tetramers (A, AA, AAAA, C, CC, and CCCC) assembled with a precise chain length specificity to form A center dot C, AA center dot CC, and AAAA center dot CCCC, which were separated by chromatography.

  DOI：

  10.1021/ja806194e
• 作为产物：
  描述：

  2'-carboxy-4,4''-bis(trimethylsilylethynyl)-5'-(1-octynyl)-1,1':3',1''-terphenyl 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 2'-carboxy-4,4''-bis(ethynyl)-5'-(1-octynyl)-1,1':3',1''-terphenyl 、 2'-carboxy-4-ethynyl-4''-trimethylsilylethynyl-5'-(1-octynyl)-1,1':3',1''-terphenyl
  参考文献：
  名称：

  带有羧基的共轭聚合物的同质双螺旋的形成和夹在链间的手性胺对大分子螺旋度的放大作用

  摘要：

  夹心胺：具有羧基的π共轭聚合物可自缔合形成消旋双螺旋。相反，与手性胺形成一个独特的单手双螺旋，其中的链通过环状氢键网络将成对的手性胺夹在中间（见图）。胺的手性信息随着螺旋手性的显着放大而转移到聚合物主链上。

  DOI：

  10.1002/anie.201301005

文献信息

• Remarkable acceleration of template-directed photodimerisation of 9-phenylethynylanthracene derivatives assisted by complementary salt bridge formation
  作者：Junki Tanabe、Daisuke Taura、Naoki Ousaka、Eiji Yashima

  DOI：10.1039/c6ob02087a

  日期：——

  acid monomers bearing a 9-phenylethynylanthracene unit at one and both ends were further investigated in the presence and absence of the complementary amidine dimer as the template. It was found that a similar photooxidation reaction of the monomers was significantly suppressed in the presence of the template even in undegassed chloroform. In addition, the template-directed photodimerisation of the mono-

  在脱气的氯仿和苯中对9-苯基乙炔基蒽的光照射不仅提供了[4 + 2]-抗Diels-Alder加成二聚体，而且还提供了[4 + 4]-抗单晶X射线分析首次发现，β-二聚体是次要产物，而蒽残基在未脱气的稀氯仿中被定量氧化，得到相应的内过氧化物。在存在和不存在互补am二聚体作为模板的情况下，进一步研究了在一端和两端带有9-苯基乙炔基蒽单元的羧酸单体的光化学反应。发现在模板存在下，即使在未脱氯的氯仿中，单体的类似光氧化反应也被显着抑制。此外，在脱气的氯仿中，单-和二-9-苯基乙炔基蒽的结合单体的模板定向光二聚反应显着加速了30倍或61倍，得到了[4 + 2]-抗-和[4 + 4]-抗-二聚体分别作为主要产物和次要产物，而在没有模板的情况下，优先使与二-9-苯基乙炔基蒽结合的单体进行光聚合。
• Complementary double‐stranded helical oligomers bearing achiral bifunctional groups that catalyze asymmetric aldol reaction
  作者：Daisuke Taura、Kouhei Shimomura、Naoki Ousaka、Eiji Yashima

  DOI：10.1002/chir.23169

  日期：2020.3

  Two novel chiral dimer and trimer strands composed of m‐terphenyl groups linked through p‐diethynylbenzene units with the chiral amidine group and achiral piperazine group introduced at the terminus or center of the strands, respectively, and its complementary achiral carboxylic acid dimer and trimer were synthesized. The complementary chiral/achiral strands form an excess‐handed double‐helical structure

  两个新型手性二聚体和三聚体链构成的米-三联苯基团通过连接p合成了分别在链末端或中心引入手性am基和非手性哌嗪基的二乙炔基苯单元，及其互补的非手性羧酸二聚体和三聚体。互补的手性/非手性链形成过度使用的双螺旋结构，在手性am基-羧酸盐盐桥偏向的共轭主链的吸收区域中，强烈的分裂型棉花效应支持了这种作用。尽管中间引入的具有催化活性的双功能哌嗪/羧酸对是非手性的，但发现双螺旋三聚体可催化环己酮与4-硝基苯甲醛的直接羟醛反应，并产生具有中等对映选择性的产物。
• Homo-double helix formation of an optically active conjugated polymer bearing carboxy groups and amplification of the helicity upon complexation with achiral and chiral amines
  作者：Wataru Makiguchi、Shinzo Kobayashi、Keisuke Furukawa、Hiroki Iida、Yoshio Furusho、Eiji Yashima

  DOI：10.1002/pola.27527

  日期：2015.4.15

  substituents through self‐association. However, upon complexation with achiral amines, such as piperidine, the CD intensity of the polymer significantly increased resulting in the formation of a greater excess one‐handed homo‐double helix via hydrogen‐bonded inclusion complexation with the achiral amines between each strand, leading to the amplification of the helicity. A preferred‐handed homo‐double

  光学活性的，米-三联苯基于π共轭高分子轴承羧基是由二乙炔单体带有羧基与（共聚合成小号，小号）-2,5-二（2-甲基丁氧基）-1,4-二溴苯使用Sonogashira反应。该共聚物在主链发色团区域显示出弱的圆二色性（CD），这是由于形成了同双螺旋结构，并且手性烷氧基取代基通过自缔合而产生了过量的螺旋手性。但是，在与非手性胺（如哌啶）络合后，聚合物的CD强度显着增加，导致通过与每条链之间的非手性胺进行氢键键合包涵体络合，形成更大的单手均双螺旋。增强螺旋度。在非外消旋胺的存在下，聚合物中还产生了优选的均一双螺旋。通过比较聚合物的CD光谱与其模型二聚体的CD光谱，研究了非手性和手性胺对均双螺旋结构的影响。©2015 Wiley Periodicals，Inc. J. Polym。科学，A部分：Polym。化学2015年，53，990-999
• Complementary double helix formation through template synthesis
  作者：Hidekazu Yamada、Yoshio Furusho、Hiroshi Ito、Eiji Yashima

  DOI：10.1039/c002170a

  日期：——

  The dimerization of carboxylic acid derivatives bearing an amino or a formyl group at one end was significantly enhanced in benzene in the presence of an optically active amidine dimer to afford a complementary double helix stabilized with salt bridges.

  在苯中，一端带有氨基或甲酰基团的羧酸衍生物在光学活性脒二聚体的存在下，其二聚化作用明显增强，从而产生了以盐桥稳定的互补双螺旋。
• Chiral Template-Directed Regio-, Diastereo-, and Enantioselective Photodimerization of an Anthracene Derivative Assisted by Complementary Amidinium–Carboxylate Salt Bridge Formation
  作者：Junki Tanabe、Daisuke Taura、Naoki Ousaka、Eiji Yashima

  DOI：10.1021/jacs.7b03317

  日期：2017.5.31

  -50 °C. Temperature-dependent inversion of the chirality of the anti-HH dimer was observed when the chiral phenylene-linked amidine dimer was used and the product ee was changed from 22% at 50 °C to -86% at -50 °C. A similar enhancement of the enantioselectivity of the anti-HH dimer was also observed for the chiral amide-linked template, producing the anti-HH dimer with up to -88% ee at -50 °C. The

  合成了一系列光学活性脒二聚体，由间三联苯骨架通过各种接头（例如非手性和手性对亚苯基和手性酰胺接头）连接而成，并用作区域-（头对尾（ HT) 或头对头 (HH))、非对映-（反或顺）和对映选择性 [4 + 4] 光环二聚反应的非手性间三联苯羧酸单体在一端带有前手性 2-取代蒽(1) 通过互补的脒-羧酸盐桥。通过对亚苯基键连接的脒二聚体在 25°C 时几乎完全提供手性顺式 HT 和抗 HH 二聚体，而通过酰胺接头连接的那些产生所有四种二聚体。对亚苯基连接的模板倾向于在高温下促进顺式-HT-光二聚体的形成，而产物对映体过量（ee）没有显着变化，而反-HH-光二聚体的形成随着温度的降低而显着增加，伴随着产品 ee 在 -50 °C 下显着提高至 -86%。当使用手性亚苯基连接的脒二聚体并且产物 ee 从 50 °C 下的 22% 变为 -50 °C 下的 -86% 时，观察到抗 HH 二聚体手性的