环己酮选择性构建功能芳烃的研究进展

doi:10.6023/cjoc202107032

摘要/Abstract

环己酮是一类廉价易得的重要的有机化工原料, 含有极性的活泼羰基, 可与亲核试剂进行亲核加成并进一步转化. 此外, 因羰基的活化作用, 其邻位的亚甲基也具有较好的反应活性. 因而, 环己酮可以作为廉价的C2源参与成环及芳构化反应构筑芳香功能分子. 将从环己酮参与的选择性构建单取代芳烃、多取代芳烃以及杂环芳烃三个方面进行阐述, 重点综述近几年环己酮与醛、酮、胺、硫酚等亲核试剂经缩合、脱氢芳构化选择性构建功能芳烃的研究进展, 并对未来进一步开发新型温和绿色的合成方法实现环己酮选择性构建功能芳烃进行了展望.

关键词: 环己酮, 亲核加成, 脱氢芳构化, 缩合, 功能芳烃

Cyclohexanone, a cheap and important organic chemical material with polar active carbonyl group, can construct many functional materials via nucleophilic addition with nucleophiles and subsequent transformation. In addition, the methylene group in the ortho-position of carbonyl group also exhibits good reactivity. Therefore, cyclohexanone can be used as a versatile C2 source for cycloaddition reaction providing various aromatic compounds via subsequent dehydroaro- matization. The cyclohexanone involved reactions to chemoselectively produce monosubstituted aromatics, polysubstituted aromatics and heterocyclic aromatics is discussed. The addition reactions and further dehydroaromatization of cyclohexanone with nucleophiles such aldehydes, ketones, aromatic amines, thiophenols and unsaturated hydrocarbons are discussed in detail as well. The environmentally benign synthesis of aromatic functional molecules with cyclohexanone is prospected at the end of this review.

Key words: cyclohexanone, nucleophilic addition, dehydroaromatization, condensation, functional aromatics

引用此文

王硕文, 姜平宇, 李镕, 杨沐阳, 邓国军. 环己酮选择性构建功能芳烃的研究进展[J]. 有机化学, 2022, 42(1): 129-146.

Shuowen Wang, Pingyu Jiang, Rong Li, Muyang Yang, Guojun Deng. Progress in Selective Construction of Functional Aromatics with Cyclohexanone[J]. Chinese Journal of Organic Chemistry, 2022, 42(1): 129-146.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 30

图式1. 环己酮非均相催化脱氢

Scheme 1. Heterogeneous catalytic dehydrogenation of cyclohexanone

图式2. 钯催化环己酮脱氢芳构化合成N-芳基磺酰胺

Scheme 2. Pd-catalyzed dehydroaromatization of cyclohexanones to synthesize N-arylsulfonamides

图式3. 钯催化环己酮脱氢芳构化合成苯酚

Scheme 3. Pd-catalyzed dehydroaromatization of cyclohexanones to synthesize phenol

图式4. 环己酮脱氢芳构化构建单取代的苯酚和芳胺

Scheme 4. Dehydroaromatization of cyclohexanones to monosubstituted phenols and aromatic amines

图式5. 环己酮非需氧型脱氢芳构化构建单取代芳胺

Scheme 5. Construction of monosubstituted aromatic amines via non-aerobic dehydroaromatization of cyclohexanones

图式6. 环己酮脱氢芳构化构建苯胺

Scheme 6. Dehydroaromatization of cyclohexanones to anilines

图式7. 环己酮构建3-取代芳基吲哚

Scheme 7. 3-Substituted aryl indole synthesis from cyclohexanones

图式8. 环己酮构建双取代2-硫醚苯酚

Scheme 8. Disubstituted 2-thioether phenol synthesis from cyclohexanones

图式9. 环己酮构建功能性儿茶酚

Scheme 9. Functional catechol synthesis from cyclohexanones

图式10. 环己酮氧化条件下构建双取代芳基邻苯二亚胺

Scheme 10. Di-substitutedaryl o-phenylenedimine synthesis from cyclohexanone under oxidizing condition

图式11. 硫促进环己酮脱氢芳构化合成芳基邻苯二亚胺

Scheme 11. Sulfur promoted dehydrogenation and aromatization of cyclohexanones to synthesize aryl o-phenylenedimine

图式12. 环己酮构建双取代苯酚

Scheme 12. Disubstituted phenol synthesis from cyclohexanone

图式13. 环己酮构建多取代3-硫醚儿茶酚

Scheme 13. Polysubstituted 3-thioether catechol formation based on cyclohexanone

图式14. 环己酮选择性构建单取代、多取代芳胺

Scheme 14. Selective construction of mono- and poly-substituted aromatic amines from cyclohexanones

图式15. 环己酮与2-氨基吡啶构建咪唑杂环

Scheme 15. Construction of imidazole heterocycles from cyclohexanones and 2-aminopyridines

图式16. 环己酮α、β位的C—H活化构建咪唑杂环

Scheme 16. Construction of imidazole heterocycles by C—H activation at α and β positions of cyclohexanones

图式17. 硫促进环己酮与2-氨基吡啶合成咪唑杂环

Scheme 17. Sulfur promotes the synthesis of imidazole heterocycles from cyclohexanone and 2-aminopyridine

图式18. 环己酮与2-氨基苯并噻唑构建咪唑杂环

Scheme 18. Construction of imidazole heterocycles with cyclohexanone and 2-aminobenzothiazole

图式19. 环己酮与苄胺构建咪唑杂环

Scheme 19. Cyclohexanone and benzylamine construction imidazole heterocycles

图式20. 环己酮与苯胺构建咔唑芳烃

Scheme 20. Carbazole synthesis from cyclohexanones and anilines

图式21. 环己酮与芳基脲构建N-取代咔唑芳烃

Scheme 21. N-Substituted carbazole formation from cyclohexanones and aryl urea

图式22. 环己酮与芳胺选择性构建咔唑和吡咯杂环

Scheme 22. Selective construction of carbazole and pyrrole heterocycles from cyclohexanone and aromatic amine

图式23. 环己酮、3-硝基吲哚和苄胺“一锅法”构建吲哚杂环

Scheme 23. Three component formation of indole derivatives involved cyclohexanones

图式24. 环己酮脱氢芳构化选择性构建吲哚和哌啶杂环

Scheme 24. Selective construction of indole and piperidine heterocycles via dehydroaromatization of cyclohexanones

图式25. 环己酮、苯胺和α-羟基酮选择性生成1,2-二芳基吲哚

Scheme 25. Selective generation of 1,2-diaryl indoles involves cyclohexanones

图式26. 环己酮与醋酸铵选择性生成苯胺和吲哚杂环

Scheme 26. Selectively synthesis of anilines and indole heterocycles from cyclohexanones and ammonium acetate

图式27. 过渡金属钯催化下环己酮与吲哚构建吲哚并噻吩杂环化

Scheme 27. Pd-catalyzed construction of indolothiophene heterocycles from cyclohexanones and indoles

图式28. 环己酮、苯胺和单质硫“一锅法”实现吩噻嗪的合成

Scheme 28. Synthesis of phenothiazine from cyclohexanones, anilines and elemental sulfur

图式29. 碘化钠介导环己酮、芳香仲胺与硫合成吩噻嗪衍生物

Scheme 29. Sodium iodide mediated phenothiazine formation from cyclohexanones, secondary aromatic amines and sulfur

图式30. 碘促进环己酮自缩合构建二苯并呋喃衍生物

Scheme 30. Self-condensation of cyclohexanones for dibenzofuran derivatives formation

参考文献 69

[1]	Lin, C.-J.; Huang, S.-H.; Lai, N.-C.; Yang, C.-M. ACS Catal. 2015, 5, 4121. doi: 10.1021/acscatal.5b00380
[2]	Liu, T. Z.; Zhou, H.; Han, B. B.; Gu, Y. B.; Li, S. Q.; Zheng, J.; Zhong, X.; Zhuang, G.-L.; Wang, J.-G. ACS Sustainable Chem. Eng. 2017, 5, 11628. doi: 10.1021/acssuschemeng.7b02974
[3]	Wang, Y.; Zhang, J. S.; Wang, X. C.; Antonietti, M.; Li, H. R. Angew. Chem., Int. Ed. 2010, 49, 3356. doi: 10.1002/anie.201000120
[4]	Wang, W.; Liu, J. J.; Zhang, L. Chem. Ind. Eng. Prog. 2013, 32, 2156. (in Chinese)
	(王巍, 刘晶晶, 张龙, 化工进展, 2013, 32, 2156.)
[5]	Fang, C. X.; Yu, Y.; Wang, Y. T.; Qu, Y. X. Modern Chem. Ind. 2013, 32, 16. (in Chinese)
	(房承宣, 于泳, 王亚涛, 屈一新, 现代化工, 2013, 32, 16.)
[6]	Hu, X.-Q.; Lichte, D.; Rodstein, I.; Weber, P.; Seitz, A.-K.; Scherpf, T.; Gessner, V. H.; Gooßen, L. J. Org. Lett. 2019, 21, 7558. doi: 10.1021/acs.orglett.9b02830
[7]	Wang, C. P.; Dong, G. B. J. Am. Chem. Soc. 2018, 140, 6057. doi: 10.1021/jacs.8b03530
[8]	Wang, J; Deng, Z. X.; Wang, C. M.; Xia, P. J.; Xiao, J. A.; Xiang, H. Y.; Chen, X. Q.; Yang, H. Org. Lett. 2018, 20, 7535. doi: 10.1021/acs.orglett.8b03292
[9]	Juliane, N. B. D.; Pelin, J.; Gerbelli, B. B.; Edwards, C. J. C.; Aguilar, A. M.; Castelletto, V.; Hamley, I. W.; Alves, W. A. Langmuir 2020, 36, 2767. doi: 10.1021/acs.langmuir.0c00198 pmid: 32131599
[10]	Garg, Y.; Tanaka, F. Org. Lett. 2020, 22, 4542. doi: 10.1021/acs.orglett.0c01561
[11]	Yin, Z. Y.; Guo, J. X.; Zhang, R.; Hu, X. Y.; Borovkov, V. J. Org. Chem. 2020, 85, 10369. doi: 10.1021/acs.joc.0c00031
[12]	Kaplaneris, N.; Koutoulogenis, G.; Raftopoulou, M.; Kokotos, C. G. J. Org. Chem. 2015, 80, 5464. doi: 10.1021/acs.joc.5b00283 pmid: 25942500
[13]	Yang, C.; Zhang, K. F.; Wu, Z. J.; Yao, H. Q.; Lin, A. J. Org. Lett. 2016, 18, 5332. pmid: 27684319
[14]	Nguyen, K. D.; Kutzscher, C.; Drache, F.; Senkovska, I.; Kaskel, S. Inorg. Chem. 2018, 57, 1483. doi: 10.1021/acs.inorgchem.7b02854 pmid: 29364659
[15]	Ipatieff, V. N.; Haensel, V. J. Org. Chem. 1942, 7, 189. doi: 10.1021/jo01197a001
[16]	Nasarow, N. D. Zh. Obshch. Khim. 1952, 22, 1147.
[17]	Chen, K.; Chang, Y. P.; Gurubrahamam, R. Org. Lett. 2015, 17, 2908. doi: 10.1021/acs.orglett.5b01040
[18]	Wang, J.; Deng, Z. X.; Wang, C. M.; Xia, P. J.; Xiao, J. A.; Xiang, H. Y.; Chen, X. Q.; Yang, H. Org. Lett. 2018, 20, 7535. doi: 10.1021/acs.orglett.8b03292
[19]	Shen, L.; Xu, L.; Hou, X. H.; Liu, N.; Wu, Z. Q. Macromolecules 2018, 51, 9547. doi: 10.1021/acs.macromol.8b02088
[20]	Shen, H. C.; Zhang, L.; Chen, S. S.; Feng, J. J.; Zhang, B. W.; Zhang, Y.; Zhang, X. H.; Wu, Y. D.; Gong, L. Z. ACS Catal. 2019, 9, 791. doi: 10.1021/acscatal.8b04654
[21]	Yang, C.; Zhang, K. F.; Wu, Z. J.; Yao, H. Q.; Lin, A. J. Org. Lett. 2016, 18, 5332. pmid: 27684319
[22]	Chen, J. J.; Chang, D.; Xiao, F. H.; Deng, G.-J. Green Chem. 2018, 20, 5459. doi: 10.1039/C8GC02654H
[23]	Chen, J. J.; Meng, H. X.; Zhang, F.; Xiao, F. H.; Deng, G.-J. Green Chem. 2019, 21, 5201. doi: 10.1039/C9GC02077B
[24]	Cao, X. X.; Bai, Y.; Xie, Y. J.; Deng, G.-J. J. Mol. Catal. A: Chem. 2014, 383, 94.
[25]	Zhang, J. W.; Jiang, Q. Q.; Yang, D. J.; Zhao, X. M.; Dong, Y. L.; Liu, R. H. Chem. Sci. 2015, 6, 4674. doi: 10.1039/C5SC01044F
[26]	Shah, M.; Guo, Q. X.; Fu, Y. Catal. Commun. 2017, 89, 60. doi: 10.1016/j.catcom.2016.10.019
[27]	Taniguchi, K.; Jin, X. J.; Yamaguchi, K.; Mizuno, N. Catal. Sci. Technol. 2016, 6, 3929. doi: 10.1039/C5CY01908G
[28]	Shimomoto, Y.; Matsubara, R.; Hayashi, M. Adv. Synth. Catal. 2018, 360, 3297. doi: 10.1002/adsc.v360.17
[29]	Koizumi, Y.; Jin, X. J.; Yatabe, T. F.; Miyazaki, R.; Hasegawa, J.-Y.; Nozaki, K.; Mizuno, N.; Yamaguchi, K. Angew. Chem., Int. Ed. 2019, 58, 10893. doi: 10.1002/anie.v58.32
[30]	Lin, W.-C.; Yatabe, T. F.; Yamaguchi, K. Chem. Commun. 2021, 57, 6530. doi: 10.1039/D1CC01686E
[31]	Lu, C. G.; Huang, H. W.; Tuo, X. L.; Jiang, P. Y.; Zhang, F.; Deng, G.-J. Org. Chem. Front. 2019, 6, 2738. doi: 10.1039/C9QO00603F
[32]	Chen, Y.; Xiao, F. H.; Chen, H.; Liu, S. W.; Deng, G.-J. RSC Adv. 2014, 4, 44621. doi: 10.1039/C4RA08014A
[33]	Liang, Y.-F.; Li, X. Y.; Wang, X. Y.; Zou, M. C.; Tang, C. H.; Liang, Y. J.; Song, S.; Jiao, N. J. Am. Chem. Soc. 2016, 138, 12271. doi: 10.1021/jacs.6b07269
[34]	Xiong, M. T.; Gao, Z.; Liang, X.; Cai, P. F.; Zhu, H. P.; Pan, Y. J. Chem. Commun. 2018, 54, 9679. doi: 10.1039/C8CC05320K
[35]	Wang, Z.; Chen, X. G.; Xie, H.; Wang, D. H.; Huang, H. W.; Deng, G.-J. Org. Lett. 2018, 20, 5470. doi: 10.1021/acs.orglett.8b02387
[36]	Zeng, H. Y.; Yu, J. J.; Li, C.-J. Chem. Commun. 2020, 56, 1239. doi: 10.1039/C9CC09347H
[37]	Wu, Y.-H.; Wang, N.-X., Zhang, T.; Yan, Z.; Xu, B.-C.; Inoa, J.; Xing, Y. Adv. Synth. Catal. 2019, 361, 3008. doi: 10.1002/adsc.v361.12
[38]	Zhen Wang, Z.; Li, C.; Huang, H. W.; Deng, G.-J. J. Org. Chem., 2020, 85, 9415. doi: 10.1021/acs.joc.0c01122 pmid: 32578988
[39]	Chen, J. J.; Chang, D.; Xiao, F. H.; Deng, G.-J. Green Chem. 2018, 20, 5459. doi: 10.1039/C8GC02654H
[40]	Nguyen, T. B.; Nguyen, L. A.; Retailleau, P. Org. Lett. 2019, 21, 6570. doi: 10.1021/acs.orglett.9b02558 pmid: 31386376
[41]	Chen, J. J.; Meng, H. X.; Zhang, F.; Xiao, F. H.; Deng, G.-J. Green Chem. 2019, 21, 5201. doi: 10.1039/C9GC02077B
[42]	Lin, Y.-M.; Lu, G.-P.; Wang, R.-K.; Yi, W.-B. Org. Lett. 2016, 18, 6424. doi: 10.1021/acs.orglett.6b03324
[43]	Jiang, P. Y.; Chen, S. P.; Huang, H. W.; Hu, K.; Xia, Y.; Deng, G.-J. Green Synth. Catal. 2021, 2, 78.
[44]	Li, X.; Song, Z.-R.; Chen, X.; Cai, Y.-C.; Liu, Y.-J.; Chen, C.-X.; Peng, J.-S. Chin. J. Org. Chem. 2020, 40, 950. (in Chinese) doi: 10.6023/cjoc201909040
	(李雪, 宋子锐, 陈鑫, 蔡轶超, 刘雅婕, 陈春霞, 彭进松, 有机化学, 2020, 40, 950.) doi: 10.6023/cjoc201909040
[45]	Zhang, Y.-H.; Wu, W.-J.; Zhang, K.-X.; Li, S.-S.; Hao, W.-Y. Chin. J. Org. Chem. 2021, 41, 1982. (in Chinese)
	(张亚辉, 吴文锦, 张可心, 黎双双, 郝文燕, 有机化学, 2021, 41, 1982.) doi: 10.6023/cjoc202012007
[46]	Xie, Y. J.; Wu, J.; Che, X. Z.; Chen, Y.; Huang, H. W.; Deng, G.-J. Green Chem. 2016, 18, 667. doi: 10.1039/C5GC01978H
[47]	Nguyen, T. B.; Ermolenko, L.; Retailleau, P.; Al-Mourabit, A. Org. Lett. 2016, 18, 2177. doi: 10.1021/acs.orglett.6b00823 pmid: 27088653
[48]	Nguyena, T. B.; Retailleau, P. Adv. Synth. Catal. 2017, 359, 3843. doi: 10.1002/adsc.v359.21
[49]	Xie, Y. J.; Chen, X. G.; Wang, Z.; Huang, H. W.; Yi, B.; Deng, G.-J. Green Chem. 2017, 19, 4294. doi: 10.1039/C7GC02014G
[50]	Chen, X. G.; Wang, Z.; Huang, H. W.; Deng, G. J. Adv. Synth. Catal. 2018, 360, 4017. doi: 10.1002/adsc.v360.20
[51]	Wen, L. X.; Tang, L.; Yang, Y.; Zha, Z. G.; Wang, Z. Y. Org. Lett. 2016, 18, 1278. doi: 10.1021/acs.orglett.6b00193
[52]	Wu, J.; Xie, Y. J.; Chen, X. G.; Deng, G.-J. Adv. Synth. Catal. 2016, 358, 3206. doi: 10.1002/adsc.201600673
[53]	Wu, J.; Chen, X. G.; Xie, Y. J.; Guo, Y. J.; Zhang, Q.; Deng, G.-J. J. Org. Chem. 2017, 82, 5743. doi: 10.1021/acs.joc.7b00556
[54]	Zhang, L.-B.; Zhu, M.-H.; Ni, S.-F.; Wen, L.-R.; Li, M. ACS Catal. 2019, 9, 1680. doi: 10.1021/acscatal.8b04933
[55]	Yang, X.; Luo, G. Y.; Zhou, L. J.; Liu, B.; Zhang, X. L.; Gao, H.; Jin, Z. C.; Chi, Y. G. R. ACS Catal. 2019, 9, 10971. doi: 10.1021/acscatal.9b03163
[56]	Yu, R.-R.; Fang, X.-J. Chin. J. Org. Chem. 2021, 41, 2532. (in Chinese) doi: 10.6023/cjoc202100048
	(余融融, 方显杰, 有机化学, 2021, 41, 2532.) doi: 10.6023/cjoc202100048
[57]	Santhini, P. V.; Krishnan R, A.; Babu, S. A.; Simethy, B. S.; Das, G.; Praveen, V. K.; Sunil Varughese, S.; John, J. J. Org. Chem. 2017, 82, 10537. doi: 10.1021/acs.joc.7b02039 pmid: 28910533
[58]	Santhini, P. V.; Babu, S. A.; Krishnan R, A.; Suresh, E.; John, J. Org. Lett. 2017, 19, 2458. doi: 10.1021/acs.orglett.7b01147 pmid: 28440656
[59]	Chen, J. J.; Chang, D.; Xiao, F. H.; Deng, G.-J. J. Org. Chem. 2019, 84, 568. doi: 10.1021/acs.joc.8b02410
[60]	Li, C.; Xie, Y. J.; Xiao, F. H.; Huang, H. W.; Deng, G.-J. Chem. Commun. 2019, 55, 4079. doi: 10.1039/C9CC00943D
[61]	Maeda, K.; Matsubara, R.; Hayashi, M. Org. Lett. 2021, 23, 1530. doi: 10.1021/acs.orglett.0c04056
[62]	Hong Sik Han, H. S.; Oh, E. H.; Jung, Y.-S.; Han, S. B. Org. Lett. 2018, 20, 1698. doi: 10.1021/acs.orglett.8b00648 pmid: 29569444
[63]	Shah, T. K.; Medina, J. M.; Garg, N. K. J. Am. Chem. Soc. 2016, 138, 4948. doi: 10.1021/jacs.6b01986
[64]	Iwasaki, M.; Kazao, Y.; Ishida, T.; Nishihara, Y. Org. Lett. 2020, 22, 7343. doi: 10.1021/acs.orglett.0c02671
[65]	Xing, H.-C.; Xie, P.-Z. Chin. J. Org. Chem. 2021, 41, 431. (in Chinese) doi: 10.6023/cjoc2021006
	(邢慧聪, 解沛忠, 有机化学, 2021, 41, 431.) doi: 10.6023/cjoc2021006
[66]	Liao, Y. F.; Peng, Y.; Qi, H. R.; Deng, G.-J.; Gong, H.; Li, C.-J. Chem. Commun. 2015, 51, 1031. doi: 10.1039/C4CC08370A
[67]	Chen, J. J.; Li, G. Z.; Xie, Y. J.; Liao, Y. F.; Xiao, F. H.; Deng, G.-J. Org. Lett. 2015, 17, 5870. doi: 10.1021/acs.orglett.5b03058
[68]	Chen, Q. H.; Xie, R.; Jia, H. H.; Sun, J. L.; Lu, G. P.; Jiang, H. F.; Zhang, M. J. Org. Chem. 2020, 85, 5629. doi: 10.1021/acs.joc.0c00562
[69]	Jiang, P. Y.; Chen, S. P.; Xia, Y.; Zhang, Q. Q.; Deng, G.-J. Org. Lett. 2020, 22, 8076. doi: 10.1021/acs.orglett.0c03023