配位导向下烯基同碳位C—H官能团化反应进展

doi:10.6023/cjoc202202028

摘要/Abstract

配位导向下烯基C—H官能团化是制备多取代烯烃的常用方法, 反应通常经历弱配位基团(羟基、酰胺、羧酸、胺基等)协助下的双键在环内的金属杂环中间体(endo-metallocycle), 实现导向基邻碳位C—H官能团化, 表现出了优异的Z/E选择性, 目前发展的C—H官能团化类型丰富, 包括烯基化、烷基化、芳基化、炔基化、烯丙基化、杂原子化和多米诺环化等. 相比较而言, 导向基同碳位烯基C—H官能团化则发展缓慢, 可能是该反应需要经历更加不稳定的双键在环外的金属杂环中间体(exo-metallocycle), 严重阻碍了烯烃的配位C—H活化的发展. 近年来, 若干课题组在这方面报道了导向基同碳位烯基C—H官能团化, 包括烯基化、烯丙基化、芳基化、碘代、炔基化反应. 按C—H官能化类型介绍了配位导向下同碳位烯基C—H官能团化反应的研究进展, 并对该领域的发展前景进行了总结与展望.

关键词: 过渡金属催化, 烯烃, 导向基, 同碳位, 邻碳位, C—H官能团化

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

引用此文

王亚洲, 祝宇航, 徐丽霞, 贺瑞, 张坚. 配位导向下烯基同碳位C—H官能团化反应进展[J]. 有机化学, 2022, 42(7): 2000-2014.

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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图/表 19

图1. 基团导向烯基C—H官能团化.

Figure 1. Directed alkenyl C—H functionalization

图2. 钯催化8-氨基喹啉酰胺导向C(烯基)—H烯基化

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

图3. 钯催化烯丙醇区域选择性C(烯基)—H烯基化

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

图4. 钯催化吡啶酰胺导向丙二烯C(烯基)—H烯基化

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

图5. 钯催化芳基烯烃区域选择性C(烯基)—H烯基化合成1,3-二烯

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

图6. 钯催化吡啶酰胺导向苯乙烯C(烯基)—H双烯基化合成三烯

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

图7. 由苯甲酸合成邻烷基取代的苯乙烯衍生物

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

图8. 钯催化羧基导向前芳族C(烯基)—H烯基化合成1,3-二烯

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

图9. 钯催化烯醇C(烯基)—H烯基化

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

图10. 钯催化氨基甲酸酯的C—H烯基化

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

图11. 钯催化酰胺C(烯基)—H烯基化反应

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

图12. 铑(III)催化烯丙醇C(烯基)—H烯基化

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

图13. 铑(III)催化烯丙醇C(烯基)—H丙二烯基化

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

图14. 钯催化双齿辅助酰胺C(烯基)—H烯丙基化

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

图15. 烯烃分子内C(烯基)—H芳基化合成肽大环化合物

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

图16. Pd/NBE协同催化下的远程C(烯基)—H官能化

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

图17. 钯催化的未活化烯烃的C(烯基)—H炔基化

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

图18. 钯催化烯丙醇区域选择性C(烯基)—H炔基化

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

图19. 钯催化(Z)-烯烃C(烯基)—H碘化反应

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

参考文献 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