Recent Advances about Protoboration of Conjugated Dienes

doi:10.6023/cjoc202105058

Abstract

The protoboration of conjugated diene is a kind of important strategy for the synthesis of allylic borides and homo-allylic borides, because of mild reaction conditions and wide functional group compatibility. Till now, several research groups have been reported key progress in this field, some of them could well control the chemical selectivity, regioselectivity and enantioselectivity of these transformations. In addition, some efficient tandem reactions which based on highly efficient protoboronation have been designed. These methods could be used for the synthesizing bioactive molecules via novel route. Furthermore, recently, the protoboronation of conjugated diene without transition metal catalyst has been realized. The research progress about protoboration of conjugated diene is summarized, the range of substrate scope is introduced, and the reaction mechanism for each reaction is discussed.

Key words: conjugated diene, protoboration, regioselectivity, enantioselectivity

Cite this article

Chenchen Zou, Changhao Niu, Xinyu Liu, Chun Zhang. Recent Advances about Protoboration of Conjugated Dienes[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4240-4254.

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Fig. & Tab. 30

Table 1. Copper(I)-catalyzed asymmetric monoborylation of 1,3-dienes reported by Ito group

Scheme 1. Reaction mechanism of copper(i)-catalyzed asymmetric monoborylation of 1,3-dienes

Table 2. Copper-catalyzed protoboration of 1,2-dihydropyridines

Table 3. Copper-catalyzed asymmetric protoboronation of 1,2- dihydroquinolines

Table 4. Copper-catalyzed protoboration of pyrrole and tandem reaction

Scheme 2. Possible reaction mechanism of copper-catalyzed protoboration of pyrrole

Scheme 3. 1,6-Protoboration of acyclic α,β,γ,δ-unsaturated ketones

Table 5. Copper-catalyzed protoboration of borylated dendralenes

Scheme 4. Possible reaction mechanism of copper-catalyzed protoboration of dendralenes

Table 6. Ligand-controlled Cu-catalyzed chemo-, regio-, and enantio-selective protoboronation

Table 7. Protoboronation of acyclic α,β,γ,δ-unsaturated ketones/esters

Table 8. Protoboronation of cyclic α,β,γ,δ-unsaturated ketones

Table 9. Copper-catalyzed protoboronation of conjugated borate diene

Scheme 5. Reaction mechanism of copper-catalyzed 1,4-protobornation of conjugated borate diene

Table 10. Copper-catalyzed stereoselective synthesis of bisboron

Table 11. Copper-catalyzed enantioselective synthesis of 6- member-oxaboranoic acid

Scheme 6. Transition state analysis about the formation of 6-member-oxaboranoic acid

Table 12. Study of protoboronation and further asymmetric transformation

Table 13. Copper-catalyzed highly selective reduction and functionalization of 1,3-diene

Table 14. Copper-catalyzed highly regioselective 1,2-hydrocarboxylation of 1,3-diene with carbon dioxide

Scheme 7. Reaction mechanism of copper-catalyzed highly regioselective 1,2-hydrocarboxylation of 1,3-diene with carbon dioxide

Table 15. Copper and palladium co-catalyzed the highly regioselective hydroarylation reaction of terminal 1,3-diene

Scheme 8. Reaction mechanism of Cu and Pd co-catalyzed highly regioselective hydroarylation of 1,3-diene

Table 16. Copper-catalyzed protoboration of CF3-containing 1,3- conjugated dienes

Table 17. Copper-catalyzed enantioselective protoboration of CF3-containing 1,3-dienes

Table 18. Copper-catalyzed highly enantioselective 1,4-protoboration of 1,3-dienes

Table 19. Cu-catalyzed protoboronation of 2-substituted 1,3-dienes

Table 20. Copper-catalyzed enantioselective 1,6-protoboronation of α,β,γ,δ-unsaturated carbonyl compounds

Table 21. Transition-metal-free triboration of trans-1-aryl-1,3-dienes

Table 22. Transition-metal-free 1,4-hydroboration of trans-1,3-dienes

References 28

[1]	(a) Ji, Y.; Zhang, M.; Xing, M.; Cui, H.; Zhao, Q.; Zhang, C. Chin. J. Chem. 2021, 39, 391. doi: 10.1002/cjoc.v39.2
	(b) Wang, H.; Jing, C.; Noble, A.; Aggarwal, V. K. Angew. Chem., nt. Ed. 2020, 59, 16859.
	(c) Wang, M.; Shi, Z. Chem. Rev. 2020, 120, 7348. doi: 10.1021/acs.chemrev.9b00384
	(d) Diner, C.; Szabó, K. J. J. Am. Chem. Soc. 2017, 139, 2-14. doi: 10.1021/jacs.6b10017
[2]	Satoh, M.; Nomoto, Y.; Miyaura, N.; Suzuki, A. Tetrahedron Lett. 1989, 30, 3789. doi: 10.1016/S0040-4039(01)80656-0
[3]	Wu, J. Y.; Moreau, B.; Ritter, T. J. Am. Chem. Soc. 2009, 131, 12915. doi: 10.1021/ja9048493
[4]	Sasaki, Y.; Zhong, C.; Sawamura, M.; Ito, H. J. Am. Chem. Soc. 2010, 132, 1226. doi: 10.1021/ja909640b
[5]	Kubota, K.; Hayama, K.; Iwamoto, H.; Ito, H. Angew. Chem., nt. Ed. 2015, 54, 8809
[6]	Kubota, K.; Watanabe, Y.; Hayama, K.; Ito, H. J. Am. Chem. Soc. 2016, 138, 4338. doi: 10.1021/jacs.6b01375 pmid: 26967578
[7]	Kubota, K.; Watanabe, Y.; Hayama, K.; Ito, H. Adv. Synth. Catal. 2016, 358, 2379. doi: 10.1002/adsc.201600372
[8]	(a) Hayama, K.; Kubota, K.; Iwamoto, H.; Ito, H. Chem. Lett., 2017, 46, 1800. doi: 10.1246/cl.170825
	(b) Hayama, K.; Kojima, R.; Kubota, K.; Ito, H. Org. Lett. 2020, 22, 739. doi: 10.1021/acs.orglett.9b04581
[9]	Luo, Y.; Wales, S. M.; Korkis, S. E.; Lam, H. W. Chem.-Eur. J., 2018, 24, 8315. doi: 10.1002/chem.v24.33
[10]	Chaves-Pouso, A.; Rivera-Chao, E.; Fananas-Mastral, M. Chem. Commun, 2020, 56, 12230. doi: 10.1039/D0CC04018E
[11]	Desfeux, C.; Besnard, C.; Mazet, C. Org. Lett. 2020, 22, 8181. doi: 10.1021/acs.orglett.0c01892
[12]	Kitanosono, T.; Xu, P.; Kobayashi, S. Chem. Commun. 2013, 49, 8184. doi: 10.1039/c3cc44324h
[13]	Gao, S.; Wang, M. Z.; Chen, M. Org. Lett. 2018, 20, 7921. doi: 10.1021/acs.orglett.8b03483
[14]	Gao, S.; Chen, M. Chem. Commun., 2019, 55, 11199. doi: 10.1039/C9CC04787E
[15]	Chen, J. C.; Chen, M. Org. Lett. 2020, 22, 7321. doi: 10.1021/acs.orglett.0c02657
[16]	Liu, J. M.; Chen, M. Org. Lett. 2020, 22, 8967. doi: 10.1021/acs.orglett.0c03366
[17]	Li, Q. F.; Jiao, X. Y.; Xing, M. M.; Zhang, P. L.; Zhao, Q.; Zhang, C. Chem. Commun. 2019, 55, 8651. doi: 10.1039/C9CC04011K
[18]	Zhang, P. L.; Zhou, Z. L.; Zhang, R. M.; Zhao, Q.; Zhang, C. Chem. Commun. 2020, 56, 11469. doi: 10.1039/D0CC05056C
[19]	Zhang, R. M.; Li, Q. F.; Zhang, M.; Chai, S. D.; Duan, Y. Q.; Su, J. F.; Zhao, Q.; Zhang, C. Chem. Commun. 2020, 56, 13551. doi: 10.1039/D0CC06007K
[20]	Wu, J.; Wu, H.; Li, X.; Liu, X.; Zhao, Q.; Huang, G.; Zhang, C. Angew. Chem., nt. Ed. 2021, 60, 20376.
[21]	Hu, Y.; Huang, D.; Wang, K.; Zhao, Z.; Zhao, F.; Xu, W.; Hu, Y. Chin. J. Org. Chem. 2020, 40, 1689. (in Chinese) doi: 10.6023/cjoc201912006
	(虎永琴, 黄丹凤, 王克虎, 赵转霞, 赵芳霞, 徐炜刚, 胡雨来, 有机化学, 2020, 40, 1689.) doi: 10.6023/cjoc201912006
[22]	Guan, Q.; Ji, Y.; Zhao, Q.; Zhang, C. CCS Chem. 2021, 3, 2000.
[23]	(a) Ibrahim, A. D.; Entsminger, S. W.; Fout, A. R. ACS Catal. 2017, 7, 3730. doi: 10.1021/acscatal.7b00362 pmid: 24328236
	(b) Obligacion, J. V.; Chirik, P. J. J. Am. Chem. Soc. 2013, 135, 19107. doi: 10.1021/ja4108148 pmid: 24328236
	(c) Wu, J. C.; Moreau, B.; Ritter, T. J. Am. Chem. Soc. 2009, 131, 12915; doi: 10.1021/ja9048493 pmid: 24328236
	(d) Sasaki, Y.; Zhong, C.; Sawamura, M.; Ito, H. J. Am. Chem. Soc. 2010, 132, 1226. doi: 10.1021/ja909640b pmid: 24328236
[24]	Liu, Y.; Fiorito, D.; Mazet, C. Chem. Sci. 2018, 9, 5284. doi: 10.1039/C8SC01538D
[25]	Luo, Y. F.; Roy, I. D.; Madec, A. G. E.; Lam, H. W. Angew. Chem., nt. Ed. 2014, 53, 4186.
[26]	Miralles, N.; Alam, R.; Szabo, K.; Fernández, E. Angew. Chem., nt. Ed. 2016, 55, 4303.
[27]	Davenportab, E.; Fernandez, E. Chem. Commun. 2018, 54, 10104. doi: 10.1039/C8CC06153J
[28]	Maza, R. J.; Davenport, E.; Miralles, N.; Carbó, J. J.; Fernández, E. Org. Lett. 2019, 21, 2251. doi: 10.1021/acs.orglett.9b00531

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