dimethyl-[2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl]phenyl]silane | 1438826-09-5

• 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: dimethyl-[2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl]phenyl]silane
• CAS: 1438826-09-5
• 化学式: C₁₇H₂₉BO₂Si
• 分子量: 304.313
• InChiKey: RZMKSPYARKECAM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.51
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  1-bromo-2-(prop-1-en-1-yl)benzene 在 正丁基锂 、 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 3,4,7,8-四甲基-1,10-菲罗啉 、 sodium acetate trihydrate 、 对甲苯磺酰肼 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 54.5h， 生成 dimethyl-[2-[1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propyl]phenyl]silane
  参考文献：
  名称：

  Iridium-Catalyzed Borylation of Secondary Benzylic C–H Bonds Directed by a Hydrosilane

  摘要：

  Most functionalizations of C-H bonds by main-group reagents occur at aryl or methyl groups. We describe a highly regioselective borylation of secondary benzylic C-H bonds catalyzed by an iridium precursor and 3,4,7,8-tetramethyl-1,10-phenanthroline as the ligand. The reaction is directed to the benzylic position by a hydrosilyl substituent. This hydrosilyl directing group is readily deprotected or transformed to other functional groups after the borylation reaction, providing access to a diverse set of secondary benzylboronate esters by C-H borylation chemistry.

  DOI：

  10.1021/ja403462b

文献信息

• Mechanistic Insights and the Origin of Regioselective Borylation in an Iridium-Catalyzed Alkyl C(sp³)–H Bond Functionalization
  作者：Chandan Patel、Vibin Abraham、Raghavan B. Sunoj

  DOI：10.1021/acs.organomet.6b00513

  日期：2017.1.9

  Iridium-catalyzed ortho benzylic C(sp(3))-H borylation of (2-propylphenyl)dimethylsilane, using bis-(ethylene glycolato)diborane as borylating agent, is investigated using B3LYP-D3 density functional theory. The reaction is found to proceed, first, through a very facile oxidative addition of a Si-H bond at the Ir center. This is followed by reductive elimination of ethylene-glycolborane. The subsequent C-H activation step, accompanied by elimination of another molecule of ethylene-glycolborane, leads to formation of a racemic mixture of four diastereomeric chiral iradacycle intermediates. The ensuing chirality at the metal center is accompanied by stereodifferentiation of the two enantiotopic hydrogen atoms due to steric interaction between the alkyl group and the boryl ligands. Our calculations also correctly predict the experimentally observed regioselectivity. The propensity for C-H bond activation was found to be in the order benzylic C(sp(3))-H > terminal alkyl C(sp(3))-H > ortho C(sp(2))-H of the aryl > secondary internal C(sp(3))-H bonds. This is succeeded by oxidative addition of bis(ethylene glycolato)diborane at the Ir center. The resulting Ir(III) (bpy)trisboryl species then undergoes borylation at the benzyllic carbon. The relative free energies of the transition states for C-H activation and C-B bond formation are found to be comparable.
• Iridium-Catalyzed Borylation of Secondary Benzylic C–H Bonds Directed by a Hydrosilane
  作者：Seung Hwan Cho、John F. Hartwig

  DOI：10.1021/ja403462b

  日期：2013.6.5

  Most functionalizations of C-H bonds by main-group reagents occur at aryl or methyl groups. We describe a highly regioselective borylation of secondary benzylic C-H bonds catalyzed by an iridium precursor and 3,4,7,8-tetramethyl-1,10-phenanthroline as the ligand. The reaction is directed to the benzylic position by a hydrosilyl substituent. This hydrosilyl directing group is readily deprotected or transformed to other functional groups after the borylation reaction, providing access to a diverse set of secondary benzylboronate esters by C-H borylation chemistry.