去甲咔咯的合成及其衍生化反应的进展

doi:10.6023/cjoc202202039

摘要/Abstract

近年来, 去甲咔咯由于显著的顺磁环电流、高单分子电导率、狭窄的HOMO-LUMO能隙、稳定的氧化还原性能以及特有的化学反应性, 引起了科研工作者的广泛关注. 综述了近些年去甲咔咯的不同合成方法, 重点阐述了在插入、取代、氧化还原、延伸π共轭体系四个方面的衍生化反应, 同时对去甲咔咯的发展进行了展望.

关键词: 去甲咔咯, 合成, 衍生化反应, 反芳香性

In recent years, norcorrole has attracted extensive attention of scientific researchers, owing to its distinct paratropic ring current, high single molecule conductivity, narrow HOMO-LUMO gap, stable redox performance and unique chemical reactivity. The different synthetic methods of norcorrole in recent years are reviewed, with emphasis on the derivatization reactions in four aspects: insertion, substitution, redox and extension of π conjugated system, and the development of norcorrole is prospected.

Key words: norcorrole, synthesis, derivatization, antiaromaticity

引用此文

李莎, 孙雅涵, 蒙燕葵, 李筱芳, 张少伟. 去甲咔咯的合成及其衍生化反应的进展[J]. 有机化学, 2022, 42(8): 2390-2405.

Sha Li, Yahan Sun, Yankui Meng, Xiaofang Li, Shaowei Zhang. Progress in the Synthesis and Derivatization of Norcorrole[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2390-2405.

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图/表 37

图1. 卟啉、咔咯和去甲咔咯的一般结构(粗线表示共轭途径)

Figure 1. Generic structures of porphyrin, corrole and norcorrole (the bold lines show the conjugation circuits)

图式1. 镍介导的次甲基二吡咯配合物1还原偶联得到NiII去甲咔咯2

Scheme 1. Nickel-mediated reductive homocoupling of dipyrrin complex 1 to NiII norcorrole 2

图式2. meso位芳基取代的去甲咔咯2a~2i的结构和合成

Scheme 2. Structures and synthesis of meso-aryl-substituted norcorroles 2a~2i

图式3. meso位烷基取代的去甲咔咯2j~2m的结构和合成

Scheme 3. Structures and synthesis of meso-alkyl-substituted norcorroles 2j~2m

图式4. 苯并镍(II)去甲咔咯TBNc和DBNc的合成

Scheme 4. Synthesis of NiII benzonorcorroles TBNc and DBNc

图式5. 铜去甲咔咯7的合成

Scheme 5. Synthesis of copper norcorrole 7

图式6. 无金属去甲咔咯、钯去甲咔咯和磷(V)去甲咔咯的合成

Scheme 6. Synthesis of the metal-free norcorrole, palladium norcorrole and norcorrole P(V) complex

图式7. 金属模板的分子间偶联α,α'-二溴吡咯配合物合成八吡咯11

Scheme 7. Metal-templated intermolecular homocoupling of α,α'-dibromodipyrrin complexes to octaphyrin 11

图式8. 由1形成12的浓度依赖性反应

Scheme 8. Concentration-dependent formation of 12 from 1

图式9. NiII卟啉13和NiII去甲咔咯2与稳定硅烯14的反应

Scheme 9. Reactions of NiII porphyrin 13 and NiII norcorrole 2 with stable silylene 14

图式10. 硅烯从硅环丙烷17转移到去甲咔咯2

Scheme 10. Silylene transfer from silacyclopropane 17 to norcorrole 2

图式11. NiII去甲咔咯2与原位生成的二氯卡宾的反应

Scheme 11. Reaction of NiII norcorrole 2 with in-situ-generated dichlorocarbene

图式12. 3-硝基NiII去甲咔咯与丁炔二酸二烷基酯的反应及22-R中meso位取代基的水解

Scheme 12. Reactions of 3-nitronorcorrolatonickel(II) with dialkyl acetylenedicarboxylates and hydrolysis of the meso-substituent in 22-R

图式13. NiII去甲咔咯2的胺化和26解离成单体自由基

Scheme 13. Amination of NiII norcorrole 2 and dissociation of 26 into monomer radical

图式14. 27中的单线态-三线态平衡

Scheme 14. Singlet-triplet equilibrium in 27

图式15. 在PhIO存在下去甲咔咯2和胺合成氮杂咔咯

Scheme 15. Synthesis of azacorrole from norcorrole 2 and amine with the presence of PhIO

图式16. 去甲咔咯2与氰化钾的氰化反应

Scheme 16. Cyanation of norcorrole 2 with potassium cyanide

图式17. 用苯硫醇取代去甲咔咯2

Scheme 17. Substitution of norcorrole 2 with thiophenol

图式18. 用苯硫醇和苯酚取代去甲咔咯2

Scheme 18. Substitution of norcorrole 2 with thiophenol and phenol

图式19. 氨基去甲咔咯的合成

Scheme 19. Synthesis of the amino norcorroles

图式20. 去甲咔咯2与活泼亚甲基化合物的反应

Scheme 20. Reaction of norcorrole 2 with active methylene compounds

图式21. 去甲咔咯2与N-杂环卡宾的反应

Scheme 21. Reaction of norcorrole 2 with NHC

图式22. 用亚硝酸异戊酯硝化去甲咔咯环

Scheme 22. Nitration of the norcorrole ring with isoamyl nitrite

图式23. 去甲咔咯2的溴化及溴代去甲咔咯47和48的重排

Scheme 23. Bromination of norcorrole 2 and Rearrangement of bromonorcorroles 47 and 48

图式24. 溴代去甲咔咯47和48的铃木-宫浦反应和施蒂勒反应

Scheme 24. Suzuki-Miyaura cross-coupling and Migita-Kosugi-Stille coupling of bromonorcorroles 47 and 48

图式25. 去甲咔咯2的辛溴化和辛炔基化

Scheme 25. Octabromination and octaalkynylation of norcorrole 2

图式26. 去甲咔咯2的弗里德-克拉夫茨酰化反应

Scheme 26. Friedel-Crafts acylation of norcorrole 2

图式27. 去甲咔咯的氧化

Scheme 27. Oxidation of norcorrole

图式28. 去甲咔咯2的氧化环裂解

Scheme 28. Oxidative ring cleavage of norcorrole 2

图式29. 61e的脱保护及62和62'之间酮-烯醇互变异构作用

Scheme 29. Deprotection of 61e and keto-enol tautomerization between 62 and 62'

图式30. 雷尼镍催化去甲咔咯2加氢反应

Scheme 30. Hydrogenation of norcorrole 2 by Raney Ni

图式31. 对甲苯磺酰肼催化去甲咔咯2加氢反应

Scheme 31. Hydrogenation of norcorrole 2 by TsNH2NH2

图式32. 去甲咔咯自由基阴离子的合成

Scheme 32. Synthesis of norcorrole radical anion

图式33. 去甲咔咯与腈亚胺的环加成反应

Scheme 33. Cycloaddition of iminonitriles to norcorrole

图式34. 吡啶稠合双(去甲咔咯)的合成

Scheme 34. Synthesis of pyridine-fused bis(norcorrole)

图式35. 吡啶稠合双(去甲咔咯)的共振结构

Scheme 35. Resonance forms of pyridine-fused bis(norcorrole)

图式36. 稠合去甲咔咯二元体的合成

Scheme 36. Synthesis of doubly linked norcorrole dimer

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