叔丁醇钾促进的环化和偶联反应

doi:10.6023/cjoc202203029

摘要/Abstract

在过去的几十年中, 过渡金属催化反应已经发展成为构建各类化学键非常强大的工具. 同时, 非金属促进的化学键构建反应, 由于其避免使用昂贵的金属催化剂和配体, 降低反应成本、减少环境污染, 符合绿色化学发展理念, 越来越受到合成化学家的关注. 其中, 叔丁醇钾促进的环化和偶联反应得到了迅速的发展. 概述了自2000年以来的叔丁醇钾参与的分子内环化和分子间偶联反应, 并阐明其可能的反应机理, 能帮助化学工作者们更好地了解该领域的发展状况, 同时促进该领域的发展.

关键词: 叔丁醇钾, 分子内环化, 自由基反应, 偶联反应

Over the past few decades, transition metal-catalyzed reactions have been developed into a powerful tool for building various chemical bonds. At the same time, non-metal-promoted chemical bond construction reactions have attracted more and more attention of synthetic chemists because of the avoiding of using expensive metal catalysts and ligands, resulting in the reduce of reaction costs and environmental pollution. It conforms to the concept of green chemistry development. Among them, potassium tert-butoxide-promoted cyclization and coupling reactions have been rapidly developed. The intramolecular cyclization and intermolecular coupling reactions involving potassium tert-butoxide since 2000 are summarized, and the possible reaction mechanisms are elucidated, which can help chemists better understand the development of this field and promote the development of this field.

Key words: potassium t-butoxide, intramolecular cyclization, free radical reaction, coupling reaction

引用此文

张力之, 廖永剑, 陈宁, 黄磊, 周敏. 叔丁醇钾促进的环化和偶联反应[J]. 有机化学, 2022, 42(7): 1950-1959.

Lizhi Zhang, Yongjian Liao, Ning Chen, Lei Huang, Min Zhou. Cyclization and Coupling Reactions Promoted by Potassium tert-Butoxide[J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 1950-1959.

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图/表 27

图式1. KOtBu促进的烯丙胺与酮的分子内环化

Scheme 1. Intramolecular cyclization of allylamine and ketone promoted by KOtBu

图式2. KOtBu促进的烯丙醚与酮的分子内环化

Scheme 2. Intramolecular cyclization of allyl ethers and ketones promoted by KOtBu

图式3. KOtBu促进的烯丙胺与酮的分子内环化反应机理

Scheme 3. Mechanism of the intramolecular cyclization reaction between allylamine and ketone promoted by KOtBu

图式4. 四氢异喹啉衍生物的分子内环化

Scheme 4. Intramolecular cyclization of tetrahydroisoquinoline derivatives

图式5. 四氢异喹啉衍生物的分子内环化机理验证实验

Scheme 5. Verification experiment of the intramolecular cyclization mechanism of tetrahydroisoquinoline derivatives

图式6. 化学选择性环化

Scheme 6. Chemoselective cyclization

图式7. 多米诺脱质子化-环化-脱水历程

Scheme 7. Deprotonation-cyclization-dehydration process of domino

图式8. KOtBu催化环化炔醇

Scheme 8. KOtBu catalyzes the cyclization of alkynyl alcohol

图式9. KOtBu催化炔胺环化

Scheme 9. KOtBu catalyzes the cyclization of alkynamine

图式10. KOtBu催化的炔醇或炔胺环化反应机理

Scheme 10. Cyclization reaction mechanism of alkynol or alkynamine catalyzed by KOtBu

图式11. Gilson合成苯二氮?

Scheme 11. Gilson synthesis of benzodiazepine

图式12. Gilson合成苯二氮?的机理

Scheme 12. Mechanism of Gilsonʼs synthesis of benzodiazepines

图式13. KOtBu和联吡啶促进的烯基碘化物分子内环化

Scheme 13. Intramolecular cyclization of alkenyl iodide promoted by KOtBu and bipyridine

图式14. 取代芳烃中的芳构化

Scheme 14. Aromatization in substituted aromatics

图式15. 合成2-乙酰基苯并呋喃的机理

Scheme 15. Synthesis mechanism of 2-acetylbenzofuran

图式16. 芳基溴化物与酚的交叉偶联

Scheme 16. Cross-coupling of aryl bromide and phenol

图式17. 苯与邻氯苯甲醛的交叉偶联

Scheme 17. Cross-coupling of benzene and o-chlorobenzaldehyde

图式18. 2-氨基苯硫酚合成苯并噻唑

Scheme 18. Synthesis of benzothiazole from 2-aminothiophenol

图式19. 烯烃与醛, TBHP和KOtBu的氧化偶联

Scheme 19. Oxidative coupling of olefins and aldehydes, TBHP and KOtBu

图式20. 氧化偶联机理

Scheme 20. Oxidative coupling mechanism

图式21. KOtBu促进的联芳基偶联

Scheme 21. Biaryl coupling promoted by KOtBu

图式22. 苯甲醛和吲哚交叉偶联

Scheme 22. Cross-coupling of benzaldehyde and indole

图式23. 双(吲哚基)芳基甲烷合成的控制实验

Scheme 23. Control experiment for the synthesis of bis(indolyl)arylmethane

图式24. DMEDA催化未活化芳烃直接芳构化

Scheme 24. Direct aromatization of unactivated aromatics catalyzed by DMEDA

图式25. 芳基碘化物与芳烃的交叉偶联

Scheme25. Cross-coupling of aryl iodide and aromatic hydrocarbon

图式26. 2-烷基氮杂芳烃的合成

Scheme 26. Synthesis of 2-alkylazaarene

图式27. 菲咯啉和KOtBu作为电子供体的前体

Scheme 27. Phenanthroline and KOtBu as precursors of electron donors

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