导向基团辅助过渡金属催化间位碳氢官能化研究进展

doi:10.6023/cjoc201903029

摘要/Abstract

碳氢键活化是目前非常活跃的研究领域之一，然而实现碳氢键位点选择性活化是该领域面临的挑战之一.以辅助基团作为导向基，实现碳氢键间位活化引起了众多学者的极大关注，经常采用的策略包括模板导向、降冰片烯介导和配体的次级效应.对近年来通过导向基团进行的间位碳氢键活化的研究进行了详细的综述，总结了目前存在的问题，并对今后的发展方向进行了展望.

关键词: 模板导向, 间位活化, 碳氢官能化, 次级效应, 瞬时介导

Transition-metal-catalyzed functionalization of unactivated C-H bonds is a highly attractive strategy for the synthesis of organic molecules, however, regioselective control is a central challenge in this field. The directing group assisted C-H functionalizations such as the use of directing templates and transient mediator, secondary interaction have attracted more attentions from researchers. The meta-C-H functionalizatioin assisted by directing groups are summarized in details. The existing problems and limitations of this field are also included. Finally, the development trend of this area is prospected.

Key words: directed by template, meta-activation, C-H functionalization, secondary interaction, transient mediator

引用此文

吴梅, 黄新平, 张海兵, 李鹏飞. 导向基团辅助过渡金属催化间位碳氢官能化研究进展[J]. 有机化学, 2019, 39(11): 3114-3131.

Wu Mei, Huang Xinping, Zhang Haibing, Li Pengfei. Advances on Directing-Group Assisted meta-C-H Functionalization Catalyzed by Transition Metal[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3114-3131.

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图/表 20

图 1. U型模板及模板导向间位活化过渡态

Figure 1. U template and transition state of meta-C—H activation

图 2. 苄基醚间位碳氢活化过渡态和Ψ3

Figure 2. Transition state of benzyl ether derivatives of meta- C—H activation and Ψ3

图 3. 3-苯基丙酸间位碳氢活化过渡态

Figure 3. meta-C—H activation transition state of 3-phenyl- propanoic acid derivatives

图式 1. 苯酚和3-苯基丙酸间位芳基化反应

Scheme 1. Meta-arylation of 3-phenylpropanoic acid and phenolic derivatives

图式 2. 苄磺酸酯间位烯烃化

Scheme 2. meta-Olefination of benzylsulfonyl ester derivatives

图式 3. 2-苯基乙磺酸和3-苯基丙酸间位二烯烃化反应

Scheme 3. meta-Diolefination of 2-phenyl ethanesulfonic acid and 3-phenylpropanoic acid derivatives

图式 4. 苄基硅烷间位烯烃化反应

Scheme 4. meta-Olefination of benzyl silane derivatives

图式 5. 二苯基羧酸和二苯基酚间位烯烃化

Scheme 5. Meta-olefination of biphenyl phenol and biphenyl carboxylic acid derivatives

图 4. 苯基醇间位活化过渡态

Figure 4. Transition state in meta-activation of phenyl alcohols

图式 6. 嘧啶模板导向间位碳氢键活化反应

Scheme 6. meta-C—H activation directed by pyrimidine-based template

图式 7. 降冰片烯介导间位碳氢键活化反应

Scheme 7. meta-C—H activation directed by transient mediator

图式 8. 苯胺、苯酚和杂环芳胺间位芳基化反应

Scheme 8. meta-C—H arylation of phenylamine, phenol and heterocycle phenylamine

图式 9. 苄醇及其衍生物间位芳基化和乙基化

Scheme 9. meta-C—H arylation and ethylation of benzyl alcohol derivatives

图式 10. 氢键促进间位活化

Scheme 10. Hydrogen bond accelerated meta-C—H activation

图 5. 具有氢键作用力的不同取代基的配体

Figure 5. Design of ligand to accelerate the reaction

图式 11. 路易斯酸碱作用力促进间位活化

Scheme 11. Interaction between Lewis acid and base accelerated meta-C—H activation

图式 12. 静电作用力促进间位活化

Scheme 12. Electrostatic interaction accelerated meta-C—H activation

图式 13. 离子对作用力促进间位活化

Scheme 13. Ion pair accelerated meta-C—H activation

图式 14. 氢键作用力促进间位活化

Scheme 14. Hydrogen bond accelerated meta-C—H activation

图式 15. 阳离子与π键作用力导向间位活化

Scheme 15. Interaction between π bond and cationic accelerated meta-C—H activation

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