Recent Advances in Geminal-Group-Directed Alkenyl C—H Functionalization

doi:10.6023/cjoc202202028

Abstract

Vicinal group-directed alkenyl C—H functionalization provides general method toward the synthesis of multi- substituted alkenes, proceeding by the weakly coordination-group (such as hydroxyl, amide, carboxylic acid, amino group etc.) assisted endo-cyclometallation, leading to vicinal C—H functionalization with excellent E/Z selectivities, including alkenylation, alkylation, arylation, alkynylation, allylation, domino cyclization etc. In stark contrast, geminal group-directed alkenyl C—H functionalization attracted much less attentions presumably due to the difficult formation of exo-metallocyles, which greatly inhibited the development of directed alkenyl C—H functionalization. In recent years, several groups have demonstrated the importance of geminal group-directed alkenyl C—H functionalization, including alkenylation, arylation, alkynylation, allylation and iodination. The research progress is introduced according to the types of geminal C—H functionalization, and the reaction mechanisms and applications of specific reactions are discussed. The development prospects with outlook are also summarized

Key words: transition-metal-catalysis, alkenes, directing group, geminal, vicinal, C—H functionalization

Cite this article

Yazhou Wang, Yuhang Zhu, Lixia Xu, Rui He, Jian Zhang. Recent Advances in Geminal-Group-Directed Alkenyl C—H Functionalization[J]. Chinese Journal of Organic Chemistry, 2022, 42(7): 2000-2014.

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Fig. & Tab. 19

Figure 1. Directed alkenyl C—H functionalization

Figure 2. 8-Aminoquinoline-directed Pd-catalyzed alkenyl geminal C(alkenyl)—H alkenylation

Figure 3. Pd-catalyzed regioselective C(alkenyl)—H alkenylation of allylic alcohols

Figure 4. Pd-catalyzed pyridineamide-directed allene C(alkenyl)—H alkenylation

Figure 5. Pd-catalyzed regioselective C(alkenyl)—H alkenylation of aryl olefins to synthesize 1,3-dienes

Figure 6. Palladium-catalyzed pyridineamide-directed C(alkenyl)—H alkenylation of styrene to synthesize trienes

Figure 7. Synthesis of ortho-alkyl substituted styrene derivatives using benzoic acids

Figure 8. Pd-catalyzed prearomatic C(alkenyl)—H olefinization to synthesize 1,3-diene directed by carboxyl

Figure 9. Pd-catalyzed C(alkenyl)—H alkenylation of alkenyl alcohols

Figure 10. Pd-catalyzed C(alkenyl)—H alkenylation of alkenyl carbamates

Figure 11. Pd-catalyzed C(alkenyl)—H alkenylation of amides

Figure 12. Rhodium(III)-catalyzed C(alkenyl)—H alkenylation of allyl alcohol

Figure 13. Rhodium(III)-catalyzed C(alkenyl)—H allenyl of allyl alcohol

Figure 14. Pd-catalyzed bidentate auxiliary-directed C(alkenyl)—H allylation of amide

Figure 15. Synthesis of peptide macrocycles by olefinic C(alkenyl)—H arylation

Figure 16. Alkenyl C(alkenyl)—H functionalization under Pd/NBE cooperative catalysis

Figure 17. Palladium-catalyzed C(alkenyl)—H alkynylation of unactivated alkenes

Figure 18. Pd-catalyzed regioselective C(alkenyl)—H alkynylation of allylic alcohols

Figure 19. Palladium-catalyzed C(alkenyl)—H iodination of (Z)-alkenes

References 26

[1]	For selected reviews on the application of C-H activation, see: (a) Abrams, D. J.; Provencher, P. A.; Sorensen, E. J. Chem. Soc. Rev. 2018, 47, 8925. doi: 10.1039/c8cs00716k pmid: 25144592
	(b) Noisier, A. F.; Brimble, M. A. Chem. Rev. 2014, 114, 8775. doi: 10.1021/cr500200x pmid: 25144592
	(c) Baccalini, A.; Faita, G.; Zanoni, G.; Maiti, D. Chem.-Eur. J. 2020, 26, 9749. doi: 10.1002/chem.202001832 pmid: 25144592
	(d) Ren, Q.; Nie, B.; Zhang, Y.; Zhang, J. Chin. J. Org. Chem. 2018, 38, 2465. (in Chinese) doi: 10.6023/cjoc201803002 pmid: 25144592
	( 任青云, 聂飚, 张英俊, 张霁, 有机化学, 2018, 38, 2465.) pmid: 25144592
	(e) Sinha, S. K.; Zanoni, G.; Maiti, D. Asian J. Org. Chem. 2018, 7, 1178. doi: 10.1002/ajoc.201800203 pmid: 25144592
[2]	(a) Murahashi, S. J. Am. Chem. Soc. 1955, 77, 6403.
	(b) Fahey, D. R. J. Organomet. Chem. 1971, 27, 283. doi: 10.1016/S0022-328X(00)80577-X
	(c) Lewis, L. N.; Smith, J. F. J. Am. Chem. Soc. 1986, 108, 2728. doi: 10.1021/ja00270a036
[3]	Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N. Nature 1993, 366, 529. doi: 10.1038/366529a0
[4]	(a) Sambiagio, C.; Schönbauer, D.; Blieck, R.; DaoHuy, T.; Pototschnig, G.; Schaaf, P.; Wiesinger, T.; Zia, M. F.; Wencel-Delord, J.; Besset, T.; Maes, B. U. W.; Schnürch, M. Chem. Soc. Rev. 2018, 47, 6603. doi: 10.1039/c8cs00201k pmid: 30033454
	(b) Rej, S.; Ano, Y.; Chatani, N. Chem. Rev. 2020, 120, 1788. doi: 10.1021/acs.chemrev.9b00495 pmid: 30033454
[5]	(a) Yu, M.; Xie, Y.; Xie, C.; Zhang, Y. Org. Lett. 2012, 14, 2164. doi: 10.1021/ol3006997
	(b) Yao, J.; Yu, M.; Zhang, Y. Adv. Synth. Catal. 2012, 354, 3205. doi: 10.1002/adsc.201200447
	(c) Zhang, X.-S.; Zhu, Q.-L.; Zhang, Y.-F.; Li, Y.-B.; Shi, Z.-J. Chem.-Eur. J. 2013, 19, 11898. doi: 10.1002/chem.201300829
[6]	(a) Unoh, Y.; Satoh, T.; Hirano, K.; Miura, M. ACS Catal. 2015, 5, 6634. doi: 10.1021/acscatal.5b01896
	(b) Liu, Z.; Wu, J.-Q.; Yang, S.-D. Org. Lett. 2017, 19, 5434. doi: 10.1021/acs.orglett.7b02710
	(c) Yang, Y.; Qiu, X.; Zhao, Y.; Mu, Y.. Z. Shi, J. Am. Chem. Soc. 2016, 138, 495.
[7]	(a) Murai, M.; Matsumoto, K.; Takeuchi, Y.; Takai, K. Org. Lett. 2015, 17, 3102. doi: 10.1021/acs.orglett.5b01373
	(b) Zhang, Q.-W.; An, K.; Liu, L.-C.; Yue, Y.; He, W. Angew. Chem., Int. Ed. 2015, 54, 6918. doi: 10.1002/anie.201502548
	(c) Simmons, E. M.; Hartwig, J. F. J. Am. Chem. Soc. 2010, 132, 17092. doi: 10.1021/ja1086547
[8]	Wang, J. Stereoselective Alkene Synthesis, Springer Verlag, Heidelberg, New York, 2012.
[9]	Tang, S.; Liu, K.; Liu, C.; Lei, A. Chem. Soc. Rev. 2015, 44, 1070. doi: 10.1039/C4CS00347K
[10]	(a) Shang, X.; Liu, Z.-Q. Chem. Soc. Rev. 2013, 42, 3253. doi: 10.1039/c2cs35445d pmid: 33491691
	(b) Zhang, J.; Lu, X.; Shen, C.; Xu, L.; Ding, L.; Zhong, G. Chem. Soc. Rev. 2021, 50, 3263. doi: 10.1039/d0cs00447b pmid: 33491691
[11]	Liu, B.; Yang, L.; Li, P.; Wang, F.; Li, X. Org. Chem. Front. 2021, 8, 1085. doi: 10.1039/D0QO01159B
[12]	Examples for Rh-catalysis: (a) Besset, T.; Kuhl, N.; Patureau., F. W.; Glorius, F. Chem.-Eur. J. 2011, 17, 7167. doi: 10.1002/chem.201101340
	(b) Zhang, J.; Loh, T.-P. Chem. Commun. 2012, 48, 11232. doi: 10.1039/c2cc36137j
	For, Ru-catalysis.
	(c) Li., F., Yu, C.; Zhang, J.; Zhong, G. Org. Lett. 2016, 18, 4582. doi: 10.1021/acs.orglett.6b02229
	(d) Li, T.; Zhang, J.; Yu, C.; Lu, X.; Xu, L.; Zhong, G. Chem. Commun. 2017, 53, 12926. doi: 10.1039/C7CC07777G
	For Pd-catalysis: (e) Liang, Q.-J.; Yang, C.; Meng, F.-F.; Jiang, B.; Xu, Y.-H.; Loh, T.-P. Angew. Chem., Int. Ed. 2017, 56, 5091. doi: 10.1002/anie.201700559
	(f) Parella, R.; Babu, S. A. J. Org. Chem. 2015, 80, 12379. doi: 10.1021/acs.joc.5b02264
	For Ir-catalysis : (g) Meng, K.; Sun, Y.; Zhang, J.; Zhang, K.; Ji, X.; Ding, L.; Zhong, G. Org. Lett. 2019, 21, 8219. doi: 10.1021/acs.orglett.9b02935
	(h) Xu, L.; Meng, K.; Zhang, J.; Sun, Y.; Lu, X.; Li, T.; Jiang, Y.; Zhong, G. Chem. Commun. 2019, 55, 9757. doi: 10.1039/C9CC04419A
	(i) Huang, Y.; Xu, L.; Yu, F.; Shen, W.; Lu, X.; Ding, L.; Zhong, L.; Zhong, G.; Zhang, J. J. Org. Chem. 2020, 85, 7225. doi: 10.1021/acs.joc.0c00619
	For, Co-catalysis.
	(j) Li, T.; Shen, C.; Sun, Y.; Zhang, J.; Xiang, P.; Lu, X.; Zhong, G. Org. Lett. 2019, 21, 7772. doi: 10.1021/acs.orglett.9b02717
[13]	Mawo, R. Y., Mustakim, S., Young, V. G., Hoffmann, M. R.; Smoliakova, I. P. Organometallics 2007, 26, 1801. doi: 10.1021/om061132p
[14]	Liu, M.; Yang, P.; Karunananda, M. K.; Wang, Y.; Liu, P.; Engle, K. M. J. Am. Chem. Soc. 2018, 140, 5805. doi: 10.1021/jacs.8b02124
[15]	Xu, S.; Hirano, K.; Miura, M. Org. Lett. 2020, 22, 9059. doi: 10.1021/acs.orglett.0c03444
[16]	Schreib, B. S.; Son, M.; Aouane, F. A.; Baik, M.-H.; Carreira, E. M. J. Am. Chem. Soc. 2021, 143, 21705. doi: 10.1021/jacs.1c11528
[17]	Shen, C.; Zhu, Y.; Jin, S.; Xu, K.; Luo, S.; Xu, L.; Zhong, G.; Zhong, L.; Zhang, J. Org. Chem. Front. 2022, 9, 989. doi: 10.1039/D1QO01676H
[18]	Tsai, H.-C.; Huang, Y.-H.; Chou, C.-M. Org. Lett. 2018, 20, 1328. doi: 10.1021/acs.orglett.8b00064
[19]	Wang, Y.-C.; Huang, Y.-H.; Tsai, H.-C.; Basha, R.-S.; Chou, C.-M. Org. Lett. 2020, 22, 6765. doi: 10.1021/acs.orglett.0c02241
[20]	Meng, K.; Li, T.; Yu, C.; Shen, C.; Zhang, J.; Zhong, G. Nat. Commun. 2019, 10, 5109. doi: 10.1038/s41467-019-13098-1
[21]	Zhu, Y.; Chen, F.; Cheng, D.; Chen, Y.; Zhao, X.; Wei, W.; Lu, Y.; Zhao, J. Org. Lett. 2020, 22, 8786. doi: 10.1021/acs.orglett.0c03126
[22]	Shen, C.; Lu, X.; Zhang, J.; Ding, L.; Sun, Y.; Zhong, G. Chem. Commun. 2019, 55, 13582. doi: 10.1039/C9CC07466J
[23]	Han, B.; Li, B.; Qi, L.; Yang, P.; He, G.; Chen, G. Org. Lett. 2020, 22, 6879. doi: 10.1021/acs.orglett.0c02422
[24]	Wu, Z.; Fatuzzo, N.; Dong, G. J. Am. Chem. Soc. 2020, 142, 2715. doi: 10.1021/jacs.9b11479
[25]	Schreib, B. S.; Fadel, M.; Carreira, E. M. Angew. Chem., Int. Ed. 2020, 59, 7818. doi: 10.1002/anie.202000935
[26]	Schreib, B. S.; Carreira, E. M. J. Am. Chem. Soc. 2019, 141, 8758. doi: 10.1021/jacs.9b03998

配位导向下烯基同碳位C—H官能团化反应进展