2-(2-methyl-6-triethylsilanylphenyl)pyridine

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 2-(2-methyl-6-triethylsilanylphenyl)pyridine
• 英文别名: 2-[2-methyl-6-(triethylsilyl)phenyl]pyridine；Triethyl-(3-methyl-2-pyridin-2-ylphenyl)silane；triethyl-(3-methyl-2-pyridin-2-ylphenyl)silane
• 化学式: C₁₈H₂₅NSi
• 分子量: 283.489
• InChiKey: JVRYGGUAWQBBGS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.77
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-溴吡啶 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 作用下， 以 甲苯 为溶剂， 反应 20.0h， 生成 2-(2-methyl-6-triethylsilanylphenyl)pyridine
  参考文献：
  名称：

  Sequential Protocol for C(sp³)–H Carboxylation with CO₂: Transition-Metal-Catalyzed Benzylic C–H Silylation and Fluoride-Mediated Carboxylation

  摘要：

  One of the most challenging transformations in current organic chemistry is the catalytic carboxylation of a C(sp(3))-H bond using CO2 gas, an inexpensive and ubiquitous Cl source. A sequential protocol for C(sp(3))-H carboxylation by employing a nitrogen-directed, metal-assisted, C-H activation/catalytic silylation reaction in conjunction with fluoride-mediated carboxylation with CO2 was established. The carboxylation proceeded only at the benzylic C(sp(3))-Si bond, not at the aromatic C(sp(2))-Si, which is advantageous for further manipulations of the products.

  DOI：

  10.1021/ol301431d

文献信息

• Hemilabile <i>N</i>-Xylyl-<i>N</i>′-methylperimidine Carbene Iridium Complexes as Catalysts for C–H Activation and Dehydrogenative Silylation: Dual Role of <i>N</i>-Xylyl Moiety for ortho-C–H Bond Activation and Reductive Bond Cleavage
  作者：Gyeongshin Choi、Hayato Tsurugi、Kazushi Mashima

  DOI：10.1021/ja406519u

  日期：2013.9.4

  phenylpyridine were selectively formed before yielding mono-ortho-silylation products. The bis(cyclometalated)iridium complex ((Xy)C(∧)C:)(C(∧)N)IrOAc (2d) ((Xy)C(∧)C: = a cyclometalated N-xylyl-N'-methylperimidine-carbene ligand and C(∧)N = a 2-pyridylphenyl ligand), reacted with 2 equiv of Et3SiH to give an iridium hydride complex, (L(4))(C(∧)N)Ir(H)(SiEt3) (8d) (L(4) = N-CH3, N-3,5-(CH3)2C6H3 perimidine), via

  使用 (L)Ir(cod)(X) (1)（L = 一个基于 perimidine 的卡宾配体，X = OAc 和 OCOPh）配合物作为催化剂在甲苯回流条件下实现了吡啶基和亚胺基底物与三乙基硅烷的直接脱氢硅烷化降冰片烯作为氢清除剂的存在，并且以良好的产率获得了硅烷化产物。分离的双（环金属化）铱配合物，(C(∧)C:)(C(∧)N)IrOAc (2) (C(∧)C: = 环金属化的 perimidine-carbene 配体和 C(∧)N = a环金属化吡啶基-和亚胺基-连接的芳族底物）是关键中间体，其中在产生单邻甲硅烷化产物之前选择性地形成底物如苯基吡啶的环金属化五元金属环。双（环金属化）铱络合物 ((Xy)C(∧)C:)(C(∧)N)IrOAc (2d) ((Xy)C(∧)C: = 环金属化 N-二甲苯基-N' -甲基嘧啶-卡宾配体和 C(∧)N = 2-吡啶基苯基配体)，与 2 当量的
• An effective and versatile strategy for the synthesis of structurally diverse heteroarylsilanes <i>via</i> Ir(<scp>iii</scp>)-catalyzed C–H silylation
  作者：Zhi-Bo Yan、Meng Peng、Qi-Long Chen、Ka Lu、Yong-Qiang Tu、Kun-Long Dai、Fu-Min Zhang、Xiao-Ming Zhang

  DOI：10.1039/d1sc02344f

  日期：——

  spirocyclic NHC Ir(III) complex (SNIr), generating a variety of heteroarylsilanes. A significant advantage of this catalytic system is that multiple types of intermolecular C–H silylation can be achieved using one catalytic system at α, β, γ, or δ positions of heteroatoms with excellent regioselectivities. Mechanistic experiments and DFT calculations indicate that the polycyclic ligand of SNIr can form an

  在明确定义的螺环 NHC Ir( III) 络合物 (SNIr)，生成各种杂芳基硅烷。这种催化系统的一个显着优点是，在杂原子的 α、β、γ 或 δ 位置使用一个催化系统可以实现多种类型的分子间 C-H 硅烷化，并具有出色的区域选择性。机理实验和 DFT 计算表明，SNIr 的多环配体可以形成可分离的环金属化中间体，使苯基齿状化合物游离，并为激活底物提供半开放空间。通常，有利的甲硅烷基化发生在螯合杂原子的 γ 或 δ 位置，形成 5 或 6 元 C-Ir-N 环状中间体。如果在空间上禁止这种激活模式，则会在 α 或 β 位置发生甲硅烷基化。
• Ru₃(CO)₁₂-Catalyzed Silylation of Benzylic C−H Bonds in Arylpyridines and Arylpyrazoles with Hydrosilanes via C−H Bond Cleavage
  作者：Fumitoshi Kakiuchi、Kazuyuki Tsuchiya、Mitsutaka Matsumoto、Eiichiro Mizushima、Naoto Chatani

  DOI：10.1021/ja047040d

  日期：2004.10.1

  Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes

  钌催化在苄基位置的 sp3 CH 键与氢硅烷的硅烷化得到苄基硅烷。对于这种硅烷化反应，Ru3(CO)12 配合物表现出很高的催化活性。这种甲硅烷基化选择性地在甲基 CH 键上进行。对于该甲硅烷基化反应，吡啶基和吡唑基以及腙中的亚氨基可作为导向基团。包括三乙基-、二甲基苯基-、叔丁基二甲基-和三苯基硅烷在内的几种氢硅烷可用作甲硅烷基化试剂。sp2 氮原子与钌配合物的配位对于实现这种硅烷化反应很重要。
• C−H Silylation of 2‐Arylpyridine Derivatives by Using Iridium Catalyst and Phosphine‐Borane Ligand
  作者：Keita Anoyama、Gen Onodera、Tsutomu Fukuda、Masanari Kimura

  DOI：10.1002/adsc.202101476

  日期：2022.3.30

  Iridium-catalyzed ortho−C−H silylation of 2-arylpyridine derivative with hydrosilane by using phosphine-borane ligand has been developed. A variety of 2-arylpyridines could be used for this reaction to give mono- and disilylated products in 81–99% yields. In this reaction, the length of linkage between phosphorus and boron plays an important role for the reaction to proceed. We consider that the nitrogen

  已经开发了通过使用膦-硼烷配体的铱催化的2-芳基吡啶衍生物与氢硅烷的邻-C-H 甲硅烷基化。多种 2-芳基吡啶可用于该反应，以 81-99% 的收率得到单甲硅烷基化和二甲硅烷基化产物。在该反应中，磷和硼之间的键长度对反应的进行起着重要作用。我们认为 2-芳基吡啶中的氮与配体中的路易斯酸性硼配位，因此铱被导向邻位-C-H 键以将其裂解。
• Sequential Protocol for C(sp³)–H Carboxylation with CO₂: Transition-Metal-Catalyzed Benzylic C–H Silylation and Fluoride-Mediated Carboxylation
  作者：Tsuyoshi Mita、Kenichi Michigami、Yoshihiro Sato

  DOI：10.1021/ol301431d

  日期：2012.7.6

  One of the most challenging transformations in current organic chemistry is the catalytic carboxylation of a C(sp(3))-H bond using CO2 gas, an inexpensive and ubiquitous Cl source. A sequential protocol for C(sp(3))-H carboxylation by employing a nitrogen-directed, metal-assisted, C-H activation/catalytic silylation reaction in conjunction with fluoride-mediated carboxylation with CO2 was established. The carboxylation proceeded only at the benzylic C(sp(3))-Si bond, not at the aromatic C(sp(2))-Si, which is advantageous for further manipulations of the products.