(3-Bromo-5,5-dipentylbenzo[b][1]benzosilol-7-yl)-dimethyl-[2-(oxan-2-yloxymethyl)phenyl]silane | 953413-02-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3-Bromo-5,5-dipentylbenzo[b][1]benzosilol-7-yl)-dimethyl-[2-(oxan-2-yloxymethyl)phenyl]silane
• CAS: 953413-02-0
• 化学式: C₃₆H₄₉BrO₂Si₂
• 分子量: 649.859
• InChiKey: HUSPKQJRBLPUQG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.24
• 重原子数：
  41
• 可旋转键数：
  13
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3-Bromo-5,5-dipentylbenzo[b][1]benzosilol-7-yl)-dimethyl-[2-(oxan-2-yloxymethyl)phenyl]silane 在 bis(tri-tert-butylphosphine)palladium(0) 、 caesium carbonate 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 生成 (2-((5,5-dipentyl-7-(4-(p-tolyl)-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indol-7-yl)-5H-dibenzo[b,d]silol-3-yl)dimethylsilyl)phenyl)methanol
  参考文献：
  名称：

  Donor–acceptor dyes incorporating a stable dibenzosilole π-conjugated spacer for dye-sensitized solar cells

  摘要：

  合成了四种新型有机染料，包括三种基于二苯并硅啶（YS01–03）和一种基于萘的染料（YS04），并对其光物理特性和染料敏化太阳能电池（DSC）的性能进行了表征。含硅的二苯并硅啶基染料（YS01–03）在入射光子转电流效率（IPCE）和总太阳能转电能效率（η）方面优于碳基类似物的萘基染料（YS04），其中YS03具有最大体积和最为分支的电子给体基团，实现了最高的η值为5.07%，而YS04的η值仅为2.88%。为了更好地理解硅如何影响激发态氧化电位（S+/*）和吸收最大值（λmax），利用密度泛函理论（DFT）计算了染料YS01–04的平衡分子几何结构，采用B3LYP能量泛函和DGDZVP基组。结果表明，含硅染料（YS01–03）中通过联苯链接的扭转角（θ1和θ2）比不含硅的染料（YS04）扭转程度更小，从而增强了π–π*重叠，这转化为含硅染料YS01–03中的光电流增强。此外，通过不同的长程校正时间相关DFT方法，包括CAM-B3LYP、LC-BLYP、WB97XD和LC-wPBE，研究了染料YS01–04的垂直电子激发和S+/*。使用CAM-B3LYP/DGDZVP计算的结果与实验结果之间具有很好的吻合。

  DOI：

  10.1039/c2jm30978e
• 作为产物：
  描述：

  3,4-二氢-2H-吡喃 、 (2-bromo-9,9-dipentyl-9H-fluoren-7-yl)[2-(hydroxymethyl)phenyl]dimethylsilane 在 盐酸 作用下， 以94%的产率得到(3-Bromo-5,5-dipentylbenzo[b][1]benzosilol-7-yl)-dimethyl-[2-(oxan-2-yloxymethyl)phenyl]silane
  参考文献：
  名称：

  A Silicon-Based Approach to Oligoarenes by Iterative Cross-Coupling Reactions of Halogenated Organo[(2-hydroxymethyl)phenyl]dimethylsilanes

  摘要：

  Highly efficient synthesis of silyl-substituted oligoarenes with defined structures is achieved by an iterative cross-coupling reaction and deprotection sequence using organo[(2-hydroxymethyl)phenyl]dimethylsilanes. The excellent stability of the tetraorganosilicon compounds as well as mild and divergent conditions for cross-coupling and deprotection steps allows preparation of highly conjugated oligoarenylsilanes such as unsymmetrically disilylated quinquethiophenes.

  DOI：

  10.1021/ja074728s

文献信息

• Synthesis of Biaryls and Oligoarenes Using Aryl[2-(hydroxymethyl)phenyl]dimethylsilanes
  作者：Jinshui Chen、Masaaki Tanaka、Akhila K. Sahoo、Masahide Takeda、Akira Yada、Yoshiaki Nakao、Tamejiro Hiyama

  DOI：10.1246/bcsj.20090325

  日期：2010.5.15

  Through intramolecular activation, highly stable aryl[2-(hydroxymethyl)phenyl]dimethylsilanes can selectively transfer their aryl groups to effect a cross-coupling reaction with various aryl bromides and chlorides in the presence of a weak non-fluoride base and a palladium/copper catalyst. This reaction tolerates a wide range of functional groups, producing the corresponding functionalized biaryls in high yields with excellent chemoselectivity. Newly disclosed reaction conditions allow the recovery of a cyclic silyl ether in modest-to-good yields and reuse for the synthesis of the arylsilanes. The introduction of two isopropyl groups on the silicon center instead of methyl groups improves the stability and allows quantitative recovery of the silicon residue. Finally, aryl halides having an O-protected [2-(hydroxymethyl)phenyl]dimethylsilyl group cross-couple with the arylsilane reagents to give silyl-functionalized biaryls. Upon deprotection, the biaryls further react with the silylated electrophiles. The iterative cross-coupling–deprotection sequences allow rapid assembly of silylated oligoarenes. Syntheses of di- and trisilyloligoarenes are also achieved by use of orthogonal O-protecting groups.

  通过分子内活化，高度稳定的二甲基[2-（羟甲基）苯基]硅烷可以将其苯基选择性地转移到各种含有苯基卤化物的芳基溴化物和氯化物上，在非氟化弱碱和钯/铜催化剂的存在下进行交联反应。该反应耐受广泛的功能基团，以高产率和高化学选择性生成相应的功能化双芳基化合物。新披露的反应条件允许以中等至良好的产率回收环状硅醚，并可重复使用于合成芳基硅烷。在硅中心引入两个异丙基取代甲基可提高稳定性，并能定量回收硅残基。最后，拥有保护性O-[2-（羟甲基）苯基]二甲基硅烷基团的芳基卤化物与芳基硅烷反应剂交联，生成含硅功能化双芳基化合物。去保护后，双芳基化合物再与硅化亲电试剂反应。通过交叉耦合-去保护序列的迭代，可以快速组装含硅的寡芳烃。通过使用正交氧保护基团，还可以实现二硅和三硅寡芳烃的合成。
• Donor–acceptor dyes incorporating a stable dibenzosilole π-conjugated spacer for dye-sensitized solar cells
  作者：Md. Akhtaruzzaman、Yohei Seya、Naoki Asao、Ashraful Islam、Eunsang Kwon、Ahmed El-Shafei、Liyuan Han、Yoshinori Yamamoto

  DOI：10.1039/c2jm30978e

  日期：——

  Four novel organic dyes including three based on dibenzosilole (YS01–03) and one based on fluorene (YS04) were synthesized, and their photophysical properties and dye-sensitized solar cell (DSC) performances were characterized. The silicon-containing dibenzosilole-based dyes (YS01–03) were superior to the carbon analogue fluorene-based dye YS04 in incident-photon-to-current conversion efficiency (IPCE), and total solar-to-electric conversion efficiency (η), with YS03, which has the bulkiest and most branched electron donor group, achieving the highest η of 5.07% compared to 2.88% of YS04. To better understand how silicon influences the excited state oxidation potentials (S+/*) and absorption maxima (λmax), the equilibrium molecular geometries of dyes YS01–04 were calculated using density functional theory (DFT) utilizing B3LYP energy functional and DGDZVP basis set. It was shown that the torsion angles (θ1 and θ2) across the biphenyl linkages of dyes containing silicon (YS01–03) were less twisted than that of the silicon-free dye (YS04), which enhanced the π–π* overlap, and that translated into photocurrent enhancements in the silicon-containing dyes YS01–03. Moreover, the vertical electronic excitations and S+/* of dyes YS01–04 were studied using different long-range corrected time-dependent DFT methods, including CAM-B3LYP, LC-BLYP, WB97XD, and LC-wPBE at the basis set level DGDZVP. Excellent agreement between the calculated, using CAM-B3LYP/DGDZVP, and experimental results was found.

  合成了四种新型有机染料，包括三种基于二苯并硅啶（YS01–03）和一种基于萘的染料（YS04），并对其光物理特性和染料敏化太阳能电池（DSC）的性能进行了表征。含硅的二苯并硅啶基染料（YS01–03）在入射光子转电流效率（IPCE）和总太阳能转电能效率（η）方面优于碳基类似物的萘基染料（YS04），其中YS03具有最大体积和最为分支的电子给体基团，实现了最高的η值为5.07%，而YS04的η值仅为2.88%。为了更好地理解硅如何影响激发态氧化电位（S+/*）和吸收最大值（λmax），利用密度泛函理论（DFT）计算了染料YS01–04的平衡分子几何结构，采用B3LYP能量泛函和DGDZVP基组。结果表明，含硅染料（YS01–03）中通过联苯链接的扭转角（θ1和θ2）比不含硅的染料（YS04）扭转程度更小，从而增强了π–π*重叠，这转化为含硅染料YS01–03中的光电流增强。此外，通过不同的长程校正时间相关DFT方法，包括CAM-B3LYP、LC-BLYP、WB97XD和LC-wPBE，研究了染料YS01–04的垂直电子激发和S+/*。使用CAM-B3LYP/DGDZVP计算的结果与实验结果之间具有很好的吻合。
• A Silicon-Based Approach to Oligoarenes by Iterative Cross-Coupling Reactions of Halogenated Organo[(2-hydroxymethyl)phenyl]dimethylsilanes
  作者：Yoshiaki Nakao、Jinshui Chen、Masaaki Tanaka、Tamejiro Hiyama

  DOI：10.1021/ja074728s

  日期：2007.9.1

  Highly efficient synthesis of silyl-substituted oligoarenes with defined structures is achieved by an iterative cross-coupling reaction and deprotection sequence using organo[(2-hydroxymethyl)phenyl]dimethylsilanes. The excellent stability of the tetraorganosilicon compounds as well as mild and divergent conditions for cross-coupling and deprotection steps allows preparation of highly conjugated oligoarenylsilanes such as unsymmetrically disilylated quinquethiophenes.