Advances in Transition-Metal-Catalyzed Keto Carbonyl-Directed C—H Bond Functionalization Reactions

doi:10.6023/cjoc202205033

Abstract

In the past two decades, transition-metal-catalyzed keto carbonyl-directed C—H bond activation has evloved as a powerful and convenient tool for the construction of C—C and C—X (X=N, F, O) bonds at the unconventional reaction sites of ketones. Among them, keto carbonyl-directed C—H bond activation reactions catalyzed by noble metals, involving ruthenium, rhodium, palladium and iridium, have been widely explored, whilst inexpensive 3d metals, such as manganese, iron and cobalt, have gradually emerged as hotspot catalysts in keto carbonyl-directed C—H activation reactions recently. In this review, advances on transition-metal-catalyzed keto carbonyl-directed C—H bond functionalization reactions from 2014 to 2021 are summarized, which are devided by reaction categories such as alkylation, alkenylation, amidation, arylation, cyclization, and so on.

Key words: transition metals, catalysis, keto carbonyl, C—H bond functionalization, organic synthesis

Cite this article

Silin Chen, Yunhui Yang, Chao Chen, Congyang Wang. Advances in Transition-Metal-Catalyzed Keto Carbonyl-Directed C—H Bond Functionalization Reactions[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 1-16.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 29

Scheme 1. Iridium-catalyzed C—H bond branch-selective alkylation of aryl ketones

Scheme 2. Iron-catalyzed C—H bond linear alkylation of aryl ketones

Scheme 3. Ruthenium-catalyzed C—H bond alkylation of 2-/3- aroylbenzofurans with acrylates

Scheme 4. Ruthenium/Rhodium-catalyzed addition reactions of ortho C—H bond of aryl ketones to maleimides

Scheme 5. Palladium-catalyzed C(4)—H bond fluoroalkylation of indoles with hypervalent iodonium salts

Scheme 6. Rhodium/Iridium-catalyzed C—H bond alkylation of (hetero)aromatic ketones with diazo esters

Scheme 7. Iron-catalyzed ortho methylation of aromatic compounds

Scheme 8. Cobalt-catalyzed ortho alkylation of aromatic compounds

Scheme 9. Palladium-catalyzed alkenylation of distal C(sp2)—H bond

Scheme 10. Manganese-catalyzed ortho-olefination of aromatic ketones

Scheme 11. Rhodium/Ruthenium/Cobalt-catalyzed oxidative Heck-type coupling reactions

Scheme 12. Ruthenium-catalyzed ortho olefination of aromatic ketones with allyl sulfones

Scheme 13. Ruthenium-catalyzed ortho olefination of aromatic ketones with alkynes

Scheme 14. Keto carbonyl-directed C(sp2)—H amidation of arenes

Scheme 15. Keto carbonyl-directed C(sp2)—H amidation of indole derivatives

Scheme 16. Enaminone-directed C(sp2)—H amidation of arenes

Scheme 17. Keto carbonyl-directed C—H arylation of arenes with arylboronates

Scheme 18. Palladium-catalyzed C—H dehydrogenative cross coupling reaction of aromatic ketones

Scheme 19. Ruthenium-catalyzed C—H arylation of aromatic ketones formed in situ

Scheme 20. Keto carbonyl-directed C—H arylation of heteroarenes

Scheme 21. Keto carbonyl-directed intramolecular annulation via C—H activation

Scheme 22. Sequential C—H activation and annulation involving internal alkynes

Scheme 23. Sequential C—H activation and annulation catalyzed by manganese

Scheme 24. Synthesis of indene derivatives via Cobalt-cata- lyzed C—H activation

Scheme 25. Synthesis of carbazolone derivatives via Rhodium-catalyzed C—H activation

Scheme 26. Keto carbonyl-directed C—H allylation

Scheme 27. Keto carbonyl-directed C—H acylation

Scheme 28. Keto carbonyl-directed C—H fluorination

Scheme 29. Keto carbonyl-directed C—H oxygenation

References 67

[1]	(a) Zheng, Q.-Z.; Jiao, N. Tetrahedron Lett. 2014, 55, 1121. doi: 10.1016/j.tetlet.2013.12.107 pmid: 30033454
	(b) Huang, Z.; Lim, H. N.; Mo, F.; Young, M. C.; Dong, G. Chem. Soc. Rev. 2015, 44, 7764. doi: 10.1039/C5CS00272A pmid: 30033454
	(c) Sambiagio, C.; Schonbauer, D.; Blieck, R.; Dao-Huy, T.; Pototschnig, G.; Schaaf, P.; Wiesinger, T.; Zia, M. F.; Wencel- Delord, J.; Besset, T.; Maes, B. U. W.; Schnurch, M. Chem. Soc. Rev. 2018, 47, 6603. doi: 10.1039/c8cs00201k pmid: 30033454
[2]	Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N. Nature 1993, 366, 529. doi: 10.1038/366529a0
[3]	Wang, Z.; Wang, C. Green Synth. Catal. 2021, 2, 66.
[4]	Crisenza, G. E.; McCreanor, N. G.; Bower, J. F. J. Am. Chem. Soc. 2014, 136, 10258. doi: 10.1021/ja505776m pmid: 25019322
[5]	Tsuchikama, K.; Kasagawa, M.; Hashimoto, Y.-K.; Endo, K.; Shibata, T. J. Organomet. Chem. 2008, 693, 3939. doi: 10.1016/j.jorganchem.2008.09.065
[6]	Kimura, N.; Kochi, T.; Kakiuchi, F. J. Am. Chem. Soc. 2017, 139. 14849. doi: 10.1021/jacs.7b08385 pmid: 29039660
[7]	Kimura, N.; Kochi, T.; Kakiuchi, F. Asian J. Org. Chem. 2019, 8, 1115. doi: 10.1002/ajoc.201900209
[8]	Kommagalla, Y.; Srinivas, K.; Ramana, C. V. Chem.-Eur. J. 2014, 20, 7884. doi: 10.1002/chem.201400401 pmid: 24838794
[9]	Srinivas, K.; Dangat, Y.; Kommagalla, Y.; Vanka, K.; Ramana, C. V. Chem.-Eur. J. 2017, 23, 7570. doi: 10.1002/chem.201700643 pmid: 28370600
[10]	Bettadapur, K. R.; Lanke, V.; Prabhu, K. R. Org. Lett. 2015, 17. 4658. doi: 10.1021/acs.orglett.5b01810 pmid: 26348371
[11]	Sherikar, M. S.; Kapanaiah, R.; Lanke, V.; Prabhu, K. R. Chem. Commun. 2018, 54, 12113. doi: 10.1039/C8CC07006G
[12]	Han, S. H.; Kim, S.; De, U.; Mishra, N. K.; Park, J.; Sharma, S.; Kwak, J. H.; Han, S.; Kim, H. S.; Kim, I. S. J. Org. Chem. 2016, 81, 12416. doi: 10.1021/acs.joc.6b02577
[13]	Borah, A. J.; Shi, Z. Chem. Commun. 2017, 53, 3945. doi: 10.1039/C7CC01274H
[14]	Li, J.-F.; Zhao, R.-F.; Zhou, F.-Q.; She, M.-Y.; Zhang, J.; Yin, B.; Zhang, S.-Y.; Li, J.-L. Org. Chem. Front. 2019, 6, 2607. doi: 10.1039/C8QO01338A
[15]	Chen, X.; Zheng, G.; Li, Y.; Song, G.; Li, X. Org. Lett. 2017, 19, 6184. doi: 10.1021/acs.orglett.7b03099
[16]	Lee, S. H.; Kundu, A.; Han, S. H.; Mishra, N. K.; Kim, K. S.; Choi, M. H.; Pandey, A. K.; Park, J. S.; Kim, H. S.; Kim, I. S. ACS Omega 2018, 3, 2661. doi: 10.1021/acsomega.8b00179
[17]	Shang, R.; Ilies, L.; Nakamura, E. J. Am. Chem. Soc. 2016, 138, 10132. doi: 10.1021/jacs.6b06908 pmid: 27487172
[18]	Santhoshkumar, R.; Mannathan, S.; Cheng, C. H. Org. Lett. 2014, 16, 4208. doi: 10.1021/ol501904e pmid: 25099927
[19]	Li, G.; Wan, L.; Zhang, G.; Leow, D.; Spangler, J.; Yu, J. Q. J. Am. Chem. Soc. 2015, 137, 4391. doi: 10.1021/ja5126897
[20]	Hu, Y.; Zhou, B.; Chen, H.; Wang, C. Angew. Chem., Int. Ed. 2018, 57, 12071. doi: 10.1002/anie.201806287
[21]	Wang, C.; Zhang, Q. Green Synth. Catal. 2022, 3, 287.
[22]	Lanke, V.; Bettadapur, K. R.; Prabhu, K. R. Org. Lett. 2016, 18, 5496. doi: 10.1021/acs.orglett.6b02698
[23]	Bakthadoss, M.; Kumar, P. V.; Reddy, T. S. Eur. J. Org. Chem. 2017, 2017, 4439. doi: 10.1002/ejoc.201700513
[24]	Sk, M. R.; Bera, S. S.; Maji, M. S. Adv. Synth. Catal. 2019, 361, 585. doi: 10.1002/adsc.201801385
[25]	Sk, M. R.; Maji, M. S. Org. Chem. Front. 2020, 7, 19. doi: 10.1039/C9QO01164A
[26]	Elumalai, K.; Leong, W. K. Tetrahedron Lett. 2018, 59, 113. doi: 10.1016/j.tetlet.2017.11.058
[27]	(a) Li, C.; Wang, S. M.; Qin, H. L. Org. Lett. 2018, 20, 4699. doi: 10.1021/acs.orglett.8b02037
	(b) Bettadapur, K. R.; Sherikar, M. S.; Lanke, V.; Prabhu, K. R. Asian J. Org. Chem. 2018, 7, 1338. doi: 10.1002/ajoc.201800193
[28]	Dana, S.; Giri, C. K.; Baidya, M. Org. Lett. 2021, 23, 6855. doi: 10.1021/acs.orglett.1c02424
[29]	Hu, F.; Szostak, M. Chem. Commun. 2016, 52, 9715. doi: 10.1039/C6CC04537E
[30]	Kim, J.; Chang, S. Angew. Chem., Int. Ed. 2014, 53, 2203. doi: 10.1002/anie.201310544
[31]	Kong, X.; Xu, B. Org. Lett. 2018, 20, 4495. doi: 10.1021/acs.orglett.8b01770
[32]	Bera, S. S.; Sk, M. R.; Maji, M. S. Chem.-Eur. J. 2019, 25, 1806. doi: 10.1002/chem.201805376
[33]	Kim, Y.; Park, J.; Chang, S. Org. Lett. 2016, 18, 1892. doi: 10.1021/acs.orglett.6b00662
[34]	Song, Z.; Antonchick, A. P. Org. Biomol. Chem. 2016, 14, 4804. doi: 10.1039/C6OB00926C
[35]	Xu, L.; Tan, L.; Ma, D. J. Org. Chem. 2016, 81, 10476. doi: 10.1021/acs.joc.6b01856
[36]	Hande, A. E.; Prabhu, K. R. J. Org. Chem. 2017, 82, 13405. doi: 10.1021/acs.joc.7b02500
[37]	Lanke, V.; Prabhu, K. R. Chem. Commun. 2017, 53, 5117. doi: 10.1039/C7CC00763A
[38]	Chen, S.; Feng, B.; Zheng, X.; Yin, J.; Yang, S.; You, J. Org. Lett. 2017, 19, 2502. doi: 10.1021/acs.orglett.7b00730
[39]	Shi, X.; Xu, W.; Wang, R.; Zeng, X.; Qiu, H.; Wang, M. J. Org. Chem. 2020, 85, 3911. doi: 10.1021/acs.joc.9b03018
[40]	Wang, F.; Jin, L.; Kong, L.; Li, X. Org. Lett. 2017, 19, 1812. doi: 10.1021/acs.orglett.7b00583 pmid: 28358202
[41]	Shi, P.; Wang, L.; Chen, K.; Wang, J.; Zhu, J. Org. Lett. 2017, 19, 2418. doi: 10.1021/acs.orglett.7b00968
[42]	Yamamoto, T.; Yamakawa, T. RSC Adv. 2015, 5, 105829. doi: 10.1039/C5RA19810K
[43]	Ogiwara, Y.; Miyake, M.; Kochi, T.; Kakiuchi, F. Organometallics 2017, 36, 159. doi: 10.1021/acs.organomet.6b00540
[44]	Suzuki, I.; Kondo, H.; Kochi, T.; Kakiuchi, F. J. Org. Chem. 2019, 84, 12975. doi: 10.1021/acs.joc.9b01756 pmid: 31533418
[45]	Zhang, B.; Wang, H. W.; Kang, Y. S.; Zhang, P.; Xu, H. J.; Lu, Y.; Sun, W. Y. Org. Lett. 2017, 19.
[46]	Zhang, C.; Rao, Y. Org. Lett. 2015, 17, 4456. doi: 10.1021/acs.orglett.5b02115 pmid: 26322534
[47]	Bruneau, C.; Gramage-Doria, R. Adv. Synth. Catal. 2016, 358, 3847. doi: 10.1002/adsc.201600735
[48]	Paymode, D. J.; Ramana, C. V. J. Org. Chem. 2015, 80, 11551. doi: 10.1021/acs.joc.5b01932 pmid: 26461428
[49]	Yang, Y.; Gao, P.; Zhao, Y.; Shi, Z. Angew. Chem., Int. Ed. 2017, 56, 3966. doi: 10.1002/anie.201612599
[50]	Rago, A. J.; Dong, G. Green Synth. Catal. 2021, 2, 216.
[51]	Shibata, T.; Ryu, N.; Takano, H. Adv. Synth. Catal. 2015, 357, 1131. doi: 10.1002/adsc.201401163
[52]	Shinde, V. S.; Mane, M. V.; Cavallo, L.; Rueping, M. Chem.-Eur. J. 2020, 26, 8308. doi: 10.1002/chem.202001793
[53]	Zhou, S.; Wang, J.; Wang, L.; Song, C.; Chen, K.; Zhu, J. Angew. Chem., Int. Ed. 2016, 55, 9384. doi: 10.1002/anie.201603943
[54]	Zhao, Y.; Li, S.; Zheng, X.; Tang, J.; She, Z.; Gao, G.; You, J. Angew. Chem., Int. Ed. 2017, 56, 4286. doi: 10.1002/anie.201612147
[55]	Yu, Y.; Wu, Q.; Liu, D.; Hu, L.; Yu, L.; Tan, Z.; Zhu, G. J. Org. Chem. 2019, 84, 7449. doi: 10.1021/acs.joc.9b00595
[56]	Zhou, B.; Hu, Y.; Liu, T.; Wang, C. Nat. Commun. 2017, 8, 1169. doi: 10.1038/s41467-017-01262-4
[57]	Liu, T.; Hu, Y.; Yang, Y.; Wang, C. CCS Chem. 2020, 2, 749.
[58]	Huo, J.; Yang, Y.; Wang, C. Org. Lett. 2021, 23, 3384. doi: 10.1021/acs.orglett.1c00857
[59]	Dethe, D. H.; C, B. N.; Bhat, A. A. J. Org. Chem. 2020, 85, 7565. doi: 10.1021/acs.joc.0c00727
[60]	Yanagawa, M.; Harada, S.; Hirose, S.; Nemoto, T. Adv. Synth. Catal. 2021, 363, 2189. doi: 10.1002/adsc.202100098
[61]	Sk, M. R.; Bera, S. S.; Maji, M. S. Org. Lett. 2018, 20, 134. doi: 10.1021/acs.orglett.7b03440
[62]	Ali, S.; Huo, J.; Wang, C. Org. Lett. 2019, 21, 6961. doi: 10.1021/acs.orglett.9b02554
[63]	Zhang, K.; Khan, R.; Chen, J.; Zhang, X.; Gao, Y.; Zhou, Y.; Li, K.; Tian, Y.; Fan, B. Org. Lett. 2020, 22, 3339. doi: 10.1021/acs.orglett.0c00765
[64]	Lee, P. Y.; Liang, P.; Yu, W. Y. Org. Lett. 2017, 19, 2082. doi: 10.1021/acs.orglett.7b00677
[65]	Zhang, J.; Wu, M.; Fan, J.; Xu, Q.; Xie, M. Chem. Commun. 2019, 55, 8102. doi: 10.1039/C9CC03893K
[66]	Wu, Q.; Mao, Y. J.; Zhou, K.; Wang, S.; Chen, L.; Xu, Z. Y.; Lou, S. J.; Xu, D. Q. Chem. Commun. 2021, 57, 4544. doi: 10.1039/D1CC01047F
[67]	Tan, X.; Massignan, L.; Hou, X.; Frey, J.; Oliveira, J. C. A.; Hussain, M. N.; Ackermann, L. Angew. Chem., Int. Ed. 2021, 60, 13264. doi: 10.1002/anie.202017359

过渡金属催化的酮羰基导向C—H键官能化反应进展