B-(phenyldimethylsilyl)catecholborane | 166330-00-3

• 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: B-(phenyldimethylsilyl)catecholborane
• 英文别名: (2H-1,3,2-Benzodioxaborol-2-yl)(dimethyl)phenylsilane；1,3,2-benzodioxaborol-2-yl-dimethyl-phenylsilane
• CAS: 166330-00-3
• 化学式: C₁₄H₁₅BO₂Si
• 分子量: 254.168
• InChiKey: FXRZAYFYCLUHPP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.64
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  环己基丙二醇 、 B-(phenyldimethylsilyl)catecholborane 在 (S)-联萘(3,5-二甲苯基)膦 、 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Silaboration of Allenes

  摘要：

  An enantioselective silaboration of allenes was achieved using an achiral silylborane in the presence of a palladium catalyst bearing a chiral monodentate phosphine ligand. (R)-2-Bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivities in the addition of (diphenylmethylsilyl)pinacolborane to the internal C=C bond of terminal allenes at 0 degrees C, giving the corresponding beta-borylallylsilanes in high yields with high enantiomeric excesses. The enantioselectivity depended on the bulkiness of substituents of allenes: the enantiomeric excesses were found to be 91-93% ee (R = tert- and sec-alkyl), 88-90% ee (R = aryl), and 80-82% ee (R = prim-alkyl and Me) at 0 degrees C. Perfect chirality transfer was observed in the intramolecular cyclization reactions of the functionalized allylsilanes, affording highly enantioenriched cyclic alkenylboranes, which underwent Suzuki-Miyaura coupling with aryl halides.

  DOI：

  10.1021/ja063934h
• 作为产物：
  描述：

  邻苯二酚 、 (dimethylphenylsilyl)bis(diethylamino)borane 在 乙酰氯 作用下， 以 环己烷 为溶剂， 以69%的产率得到B-(phenyldimethylsilyl)catecholborane
  参考文献：
  名称：

  甲硅烷基硼烷的合成与反应性

  摘要：

  Several representative silylboranes, including B-(phenyldimethylsilyl)catecholborane (7), were prepared and their reactivity explored. The reaction of silylboranes with either vinyllithium or lithium acetylide generated the corresponding silylborates which rearrange upon treatment with I-2, producing the vinyl-silane and silyl acetylide, respectively. The reaction of 7 with ethyl diazoacetate yielded ethyl (phenyldimethylsilyl)acetate upon hydrolysis.

  DOI：

  10.1021/om00006a064

文献信息

• Regio- and stereoselective synthesis of (Z)-β-silylalkenylboranes by silaboration of alkynes catalyzed by palladium and platinum complexes
  作者：Michinori Suginome、Takanori Matsuda、Hiroshi Nakamura、Yoshihiko Ito

  DOI：10.1016/s0040-4020(99)00444-5

  日期：1999.7

  Addition of the silicon-boron bonds of (dimethylphenylsilyl)boranes having pinacol, catechol, and diethylamino groups on the boron across carbon-carbon triple bonds is effectively catalyzed by palladium complexes. The silaboration of a variety of terminal alkynes took place with almost complete regio- and stereoselectivity to afford (Z)-1-boryl-2-silylalkenes in high yields. The silaboration products

  钯配合物可有效地催化硼上具有频哪醇，邻苯二酚和二乙氨基的（二甲基苯基甲硅烷基）硼烷的硅-硼键跨碳-碳三键的加成。各种末端炔的硅烷化反应几乎完全实现了区域和立体选择性，从而以高收率提供了（Z）-1-硼基-2-甲硅烷基烯烃。将硅烷化产物与芳基碘化物和铑催化的共轭物加到甲基乙烯基酮中进行钯催化的交叉偶联反应，分别以高收率得到β-甲硅烷基苯乙烯衍生物和δ-甲硅烷基-γ，δ-不饱和酮。 。
• Palladium-Catalyzed Asymmetric Silaboration of Allenes
  作者：Toshimichi Ohmura、Hiroki Taniguchi、Michinori Suginome

  DOI：10.1021/ja063934h

  日期：2006.10.1

  An enantioselective silaboration of allenes was achieved using an achiral silylborane in the presence of a palladium catalyst bearing a chiral monodentate phosphine ligand. (R)-2-Bis(3,5-dimethylphenyl)phosphino-1,1'-binaphthyl gave the highest enantioselectivities in the addition of (diphenylmethylsilyl)pinacolborane to the internal C=C bond of terminal allenes at 0 degrees C, giving the corresponding beta-borylallylsilanes in high yields with high enantiomeric excesses. The enantioselectivity depended on the bulkiness of substituents of allenes: the enantiomeric excesses were found to be 91-93% ee (R = tert- and sec-alkyl), 88-90% ee (R = aryl), and 80-82% ee (R = prim-alkyl and Me) at 0 degrees C. Perfect chirality transfer was observed in the intramolecular cyclization reactions of the functionalized allylsilanes, affording highly enantioenriched cyclic alkenylboranes, which underwent Suzuki-Miyaura coupling with aryl halides.
• Synthesis and Reactivity of Silylboranes
  作者：John D. Buynak、Bolin Geng

  DOI：10.1021/om00006a064

  日期：1995.6

  Several representative silylboranes, including B-(phenyldimethylsilyl)catecholborane (7), were prepared and their reactivity explored. The reaction of silylboranes with either vinyllithium or lithium acetylide generated the corresponding silylborates which rearrange upon treatment with I-2, producing the vinyl-silane and silyl acetylide, respectively. The reaction of 7 with ethyl diazoacetate yielded ethyl (phenyldimethylsilyl)acetate upon hydrolysis.