新型光敏剂2, 4, 5, 6-四(9-咔唑基)间苯二腈在无金属有机光合成中的应用

doi:10.6023/cjoc201904022

摘要/Abstract

可见光促进的有机合成是近年来有机化学领域重要的研究热点和前沿.其中，廉价易得的有机染料作为光催化剂的应用引起了人们的关注.近来，2，4，5，6-四（9-咔唑基）间苯二腈（4CzIPN）作为一种新型的有机光敏剂，在可见光诱导的自由基反应中表现出优异的催化性能.主要综述了可见光诱导下4CzIPN催化的无金属有机光合成反应，介绍了4CzIPN引发不同类型自由基前体（包括硅试剂、羧酸及其衍生物、含硫试剂和氟试剂等）的光合成应用.

关键词: 2, 4, 5, 6-四(9-咔唑基)间苯二腈(4CzIPN), 有机光催化剂, 可见光诱导, 无金属

Visible-light-promoted organic synthesis is an important research hotspot and frontier in organic chemistry in recent years. Particularly, as a novel organic photosensitizer, 2, 4, 5, 6-tetrakis(carbazol-9-yl)-1, 3-dicyanobenzene (4CzIPN) has showed excellent catalytic performance in visible-light-induced radical reactions. The recent progress on the transition-metal-free photosynthesis under visible-light catalyzed by 4CzIPN is reviewed, and the application of 4CzIPN for photocatalytic organic transformations from different precursors (including silicon reagent, carboxylic acid and its derivatives, sulfur-containing reagent and fluorine reagent) is included.

Key words: 2, 4, 5, 6-tetrakis(carbazol-9-yl)-1, 3-dicyanobenzene (4CzIPN), organophotocatalyst, visible-light-induced, metal-free

引用此文

陈锦杨, 李玉涵, 梅兰, 吴红谕. 新型光敏剂2, 4, 5, 6-四(9-咔唑基)间苯二腈在无金属有机光合成中的应用[J]. 有机化学, 2019, 39(11): 3040-3050.

Chen Jinyang, Li Yuhan, Mei Lan, Wu Hongyu. Application of Photosensitizer 2, 4, 5, 6-Tetrakis(carbazol-9-yl)-1, 3-dicyanobenzene in Photo-induced Transition-Metal-Free Organic Synthesis[J]. Chinese Journal of Organic Chemistry, 2019, 39(11): 3040-3050.

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图/表 24

图 1. 2, 4, 5, 6-四(9-咔唑基)间苯二腈(4CzIPN)的结构

Figure 1. Structure of 2, 4, 5, 6-tetrakis(carbazol-9-yl)-1, 3- dicyanobenzene (4CzIPN)

^a Conditions: All the potentials are relative to SCE (saturated calomel electrode), CH₃CN, room temperature.

Compd.	E_1/2(P⁺/ P*)/V	E_1/2(P*/ P^-)/V	E_1/2(P⁺/ P)/V	E_1/2(P/ P^-)/V
4CzIPN	-1.04	+1.35	+1.52	-1.21
曙红Y	-1.11	+0.83	+0.78	-1.06
孟加拉玫瑰红	-0.99	+0.66	+0.78	-1.11
亚甲基蓝		+1.48		+0.11
10-甲基-9-均三甲苯基吖啶盐		+2.06		-0.57
啶盐

表 1. 4CzIPN与几种常见有机染料的氧化还原电位a

Table 1. Redox potentials of common organophotocatalysts

图式 1. 4CzIPN催化的自由基脱氟烷基化反应

Schema 1. 4CzIPN-catalyzed defluorinative alkylation reaction

图式 2. 4CzIPN催化的环丙烷化反应

Schema 2. 4CzIPN-catalyzed cyclopropanation reaction

图式 3. 4CzIPN催化的环丙烷化反应

Schema 3. 4CzIPN-catalyzed catalyzed cyclopropanation reaction

图式 4. 4CzIPN催化的硅氢键官能团化

Schema 4. 4CzIPN-catalyzed Si-H functionalization

图式 5. 4CzIPN催化烯烃的硅氢化反应

Schema 5. 4CzIPN-catalyzed hydrosilylation of olefins

图式 6. 4CzIPN催化的烯烃的双官能团化

Schema 6. 4CzIPN-catalyzed difunctionalization of olefins

图式 7. 4CzIPN催化亚胺的烷基化反应

Schema 7. 4CzIPN-catalyzed alkylation of imines

图式 8. 4CzIPN催化烷基自由基的羰基化反应

Schema 8. 4CzIPN-catalyzed carbonylation of alkyl radicals

图式 9. 4CzIPN催化烯烃的氢甲酰化反应

Schema 9. 4CzIPN-catalyzed hydroformylation of olefins

图式 10. 4CzIPN催化的“一锅两步”的Minisci反应

Schema 10. 4CzIPN-catalyzed one-pot stepwise Minisci reaction

图式 11. 4CzIPN催化的氧化脱羧反应

Schema 11. 4CzIPN-catalyzed oxidative decarboxylation coupling

图式 12. 4CzIPN催化的非活化烯烃双官能化反应

Schema 12. 4CzIPN-catalyzed difunctionalization of unactivated alkene

图式 13. 4CzIPN催化的脱羧偶联反应

Schema 13. 4CzIPN-catalyzed decarboxylation coupling reaction

图式 14. 4CzIPN催化叔醚的硫三氟甲基化反应

Schema 14. 4CzIPN-catalyzed trifluoromethylthiolation of tertiary ethers

图式 15. 4CzIPN催化的自由基串联环化反应

Schema 15. 4CzIPN-catalyzed radical cascade reactions

图式 16. 4CzIPN催化合成α, α-二氟酮腙

Schema 16. 4CzIPN-catalyzed synthesis of α, α-difluoroketone hydrazones

图式 17. 4CzIPN催化环化硒醚化

Schema 17. 4CzIPN-catalyzed selenation cyclization

图式 18. 4CzIPN催化合成1, 5-二羰基化合物

Schema 18. 4CzIPN-catalyzed synthesis of 1, 5-dicarbonyl compounds

图式 19. 4CzIPN催化合成氯代芳烃

Schema 19. 4CzIPN-catalyzed synthesis of chlorinated arenes

图式 20. 4CzIPN催化环状烷烃的合成

Schema 20. 4CzIPN-catalyzed synthesis of cycloalkanes

图式 21. 4CzIPN催化的远程C—H键官能化

Schema 21. 4CzIPN-catalyzed remote C—H functionalization

图式 22. 4CzIPN催化亚胺的还原羧化反应

Schema 22. 4CzIPN-catalyzed hydrocarboxylation of imines

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