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Mechanistic study of the ligand controlled regioselectivity in iridium catalyzed C- H borylation of aromatic imines

机译：铱催化C- Horylation的铱催化C- Horylation的配体控制区域选择性研究

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摘要

As a major challenge in C-H borylation, how to control the selectivity has attracted lots of attention, however, the related mechanistic information still needs to be uncovered. Herein, density functional theory (DFT) has been used to study the mechanism for the ligand controlled regioselectivity in the iridium-catalyzed C-H borylation of aromatic imines, which is inspired by experimental observations (R. Bisht, B. Chattopadhyay, J. Am. Chem. Soc., 2016, 138, 84-87). The proposed Ir(i)-Ir(iii) catalytic cycle includes (i) the oxidative addition of the C-H bond to iridium(i); (ii) the reductive elimination of a C-B bond; (iii) the oxidative addition of B(2)pin(2) to an iridium(i) hydride complex; and (iv) the reductive elimination of a B-H bond. The oxidative addition of a C-H bond to the iridium center is the determining step. For the ligand AQ, ortho-selectivity is proposed to be attributed to the decreased steric hindrance and increased electron donating effect of AQ (8-aminoquinoline) which promotes proton-transfer in the ortho-transition state of C-H activation. While, for the TMP ligand, the steric repulsion between the TMP (4,5,7,8-tetramethyl-1, 10-phenanthroline) ligand and the ortho-substituted imine hinders the ortho C-H activation and favors meta borylation. Our calculations provide insights into further ligand design to achieve different regioselective borylation of aromatics. Guided by the results, the regioselectivity in the borylation of aromatics may be achieved by accordingly modifying the electronic and steric substituents of the ligand.
机译：作为C-H Borylation中的主要挑战，如何控制选择性引起了很多关注，然而，仍然需要发现相关的机械信息。在此，密度函数理论（DFT）已经用于研究芳族丙胺催化Chorylation中的配体控制区域选择性的机制，其由实验观察（R.Bisht，B.Chattopadhyay，J.AM）的启发。化学。SoC。，2016,138,84-87）。所提出的IR（I）-Ir（III）催化周期包括（i）氧化加入铱（I）的C-H键; （ii）还原消除C-B键; （iii）氧化添加B（2）销（2）至铱（I）氢化物复合物; （iv）重新消除B-H键。向铱中心氧化加入C-H键是确定步骤。对于配体AQ，提出邻邻选择性归因于降低的空间障碍和AQ（8-氨基喹啉）的增加的电子捐献效应，其促进C-H激活的正交状态下的质子转移。虽然对于TMP配体，TMP（4,5,7,8-四甲基-1,10-菲咯啉）配体和邻氨酸亚胺之间的空间排斥阻碍了邻C-H激活和益处相色谱。我们的计算提供了进一步配体设计的见解，以实现芳烃的不同区域选择性。通过结果引导，通过相应地改变配体的电子和空间取代基，可以实现芳烃的硼化的区域选择性。

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  • 来源
    《RSC Advances》 |2018年第62期|共8页
  • 作者

    Liu Yuhua; Chen Jipei; Zhan Kangsheng; Shen Yiqiang; Gao Hui; Yao Lingmin;

  • 作者单位

    Guangzhou Univ Sch Phys &

    Elect Engn Guangzhou 510006 Guangdong Peoples R China;

    Guangzhou Univ Sch Phys &

    Elect Engn Guangzhou 510006 Guangdong Peoples R China;

    Guangzhou Univ Sch Phys &

    Elect Engn Guangzhou 510006 Guangdong Peoples R China;

    Guangzhou Univ Sch Phys &

    Elect Engn Guangzhou 510006 Guangdong Peoples R China;

    Guangzhou Med Univ Key Lab Mol Target &

    Clin Pharmacol Sch Pharmaceut Sci Guangzhou 511436 Guangdong Peoples R China;

    Guangzhou Univ Sch Phys &

    Elect Engn Guangzhou 510006 Guangdong Peoples R China;

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  • 中图分类 化学;
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