[4-(diphenylamino)phenyl][2-(hydroxymethyl)phenyl]dimethylsilane | 953412-86-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: [4-(diphenylamino)phenyl][2-(hydroxymethyl)phenyl]dimethylsilane
• 英文别名: (2-((4-(Diphenylamino)phenyl)dimethylsilyl)phenyl)methanol；[2-[dimethyl-[4-(N-phenylanilino)phenyl]silyl]phenyl]methanol
• CAS: 953412-86-7
• 化学式: C₂₇H₂₇NOSi
• 分子量: 409.603
• InChiKey: JIGJXZQBGQVASP-UHFFFAOYSA-N

物化性质

• 沸点：
  539.2±50.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.47
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  23.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [4-(diphenylamino)phenyl][2-(hydroxymethyl)phenyl]dimethylsilane 、 3-氯-2-甲基丙烯 在 正丁基锂 、 copper(l) iodide 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.5h， 以91%的产率得到[4-(2-methylprop-2-en-1-yl)phenyl]diphenylamine
  参考文献：
  名称：

  铜（I）催化烷氧基的分子内配位活化的芳基和烯基硅烷的烷基化

  摘要：

  让我们坐标：铜（I）催化的链烯基和芳基硅烷与伯烷基碘以及烯丙基和苄基卤化物如C（SP交叉耦合3）通过醇盐的分子内配位活化已经实现X电偶联伴侣。这种烷基化容许包括游离羟基在内的一系列官能团。IPr = 1,3-双（2,6-二异丙基苯基）咪唑-2-亚烷基。

  DOI：

  10.1002/anie.201306882
• 作为产物：
  描述：

  4-溴三苯胺 、 1,3-二氢-1,1-二甲基-2,1-苯并氧硅杂环戊二烯 在 magnesium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 4.0h， 以95%的产率得到[4-(diphenylamino)phenyl][2-(hydroxymethyl)phenyl]dimethylsilane
  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。
• Polyarylene Synthesis by Cross-Coupling with HOMSi Reagents
  作者：Kenta Shimizu、Yasunori Minami、Yoshiaki Nakao、Ken-ichiro Ohya、Hideyuki Ikehira、Tamejiro Hiyama

  DOI：10.1246/cl.2013.45

  日期：2013.1.5

  Cross-coupling reaction of dibromoarenes with HOMSi reagents (organo[2-(hydroxymethyl)phenyl]dimethylsilanes), or alternatively bromoarenes with arylene-bisHOMSi reagents, proceeded smoothly in the presence of a Pd catalyst and a weak base, and ter- or quaterarenes are produced in excellent yields. The present reaction was successfully applied to polyarylene synthesis using 4,7-dibromobenzothiadiazole or a 2,7-dibromofluorene derivative along with a 2,7-fluorenylene-bisHOMSi reagent.

  在钯催化剂和弱碱存在下，二溴烯烃与 HOMSi 试剂（有机[2-（羟甲基）苯基]二甲基硅烷）或溴烯烃与芳基-双 HOMSi 试剂的交叉偶联反应顺利进行，并以极好的产率生成三元烯烃或四元烯烃。本反应成功地应用于使用 4,7-二溴苯并噻二唑或 2,7-二溴芴衍生物和 2,7-芴-双 HOMSi 试剂合成聚芳醚。
• Copper(I)-Catalyzed Alkylation of Aryl- and Alkenylsilanes Activated by Intramolecular Coordination of an Alkoxide
  作者：Akira Tsubouchi、Daisuke Muramatsu、Takeshi Takeda

  DOI：10.1002/anie.201306882

  日期：2013.11.25

  Let's coordinate: Copper(I)‐catalyzed cross‐coupling of alkenyl‐ and arylsilanes with primary alkyl iodides as well as allylic and benzylic halides as C(sp3)X electrophilic coupling partners has been realized by intramolecular activation through alkoxide coordination. This alkylation tolerates a range of functional groups including a free hydroxy group. IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene

  让我们坐标：铜（I）催化的链烯基和芳基硅烷与伯烷基碘以及烯丙基和苄基卤化物如C（SP交叉耦合3）通过醇盐的分子内配位活化已经实现X电偶联伴侣。这种烷基化容许包括游离羟基在内的一系列官能团。IPr = 1,3-双（2,6-二异丙基苯基）咪唑-2-亚烷基。
• 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.