4-thiomethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaboryl)benzonitrile | 863868-24-0

• 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: 4-thiomethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaboryl)benzonitrile
• 英文别名: 4-(methylthio)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile；4-methylsulfanyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile
• CAS: 863868-24-0
• 化学式: C₁₄H₁₈BNO₂S
• 分子量: 275.179
• InChiKey: VOEJNBFZYJHHOZ-UHFFFAOYSA-N

物化性质

• 沸点：
  421.2±40.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.58
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  67.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  对甲硫基苯甲腈 、 联硼酸频那醇酯 在 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 4,4'-二叔丁基-2,2'-二吡啶 作用下， 以 对二甲苯 为溶剂， 反应 24.0h， 以68%的产率得到4-thiomethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaboryl)benzonitrile
  参考文献：
  名称：

  Iridium-Catalyzed ortho-C–H Borylation of Thioanisole Derivatives Using Bipyridine-Type Ligand

  摘要：

  A simple iridium catalytic system was developed that allows for a variety of 2-borylthioanisoles to be easily synthesized via ortho-selective C-H borylation of thioanisole derivatives. Once introduced, boryl and methylthio groups were converted by palladium-catalyzed transformations. Density functional theory calculations revealed that weak interactions, such as hydrogen bonding between the C-H bond of the SCH3 group and the oxygen atom of the boryl ligand, control the ortho-selectivity.

  DOI：

  10.1021/acs.orglett.0c00946

文献信息

• Sterically Directed Functionalization of Aromatic C−H Bonds:  Selective Borylation Ortho to Cyano Groups in Arenes and Heterocycles
  作者：Ghayoor A. Chotana、Michael A. Rak、Milton R. Smith

  DOI：10.1021/ja0428309

  日期：2005.8.1

  Ir-catalyzed borylations of 4-substituted benzonitriles are described. In contrast to electrophilic aromatic substitutions and directed ortho metalations, C-H activation/borylation enables functionalization at the 2-position, adjacent to the cyano group, when the 4-subsitutent is larger than cyano. When an excess of borane reagent is used, diborylation can be achieved with a single regioisomer being

  描述了 4-取代苄腈的 Ir 催化硼化。与亲电芳香取代和定向邻位金属化相反，当 4-取代基大于氰基时，CH 活化/硼酸化能够在与氰基相邻的 2-位进行官能化。当使用过量的硼烷试剂时，在某些情况下可以通过形成单一区域异构体来实现二硼化。还报道了空间定向硼酸化扩展到氰基取代的五元和六元环杂环。