Progress in Selective Construction of Functional Aromatics with Cyclohexanone

doi:10.6023/cjoc202107032

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 30

Scheme 1. Heterogeneous catalytic dehydrogenation of cyclohexanone

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

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

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

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

Scheme 6. Dehydroaromatization of cyclohexanones to anilines

Scheme 7. 3-Substituted aryl indole synthesis from cyclohexanones

Scheme 8. Disubstituted 2-thioether phenol synthesis from cyclohexanones

Scheme 9. Functional catechol synthesis from cyclohexanones

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

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

Scheme 12. Disubstituted phenol synthesis from cyclohexanone

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

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

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

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

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

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

Scheme 19. Cyclohexanone and benzylamine construction imidazole heterocycles

Scheme 20. Carbazole synthesis from cyclohexanones and anilines

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

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

Scheme 23. Three component formation of indole derivatives involved cyclohexanones

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

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

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

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

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

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

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

References 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

环己酮选择性构建功能芳烃的研究进展