Catalyst-Free and Solvent-Free Hydroboration of Alkynes and Alkenes with Catecholborane

doi:10.6023/cjoc202209011

Abstract

A catalyst-free and solvent hydroboration of alkynes and alkenes with catecholborane was reported. Various alkynes and alkenes including aromatic and aliphatic groups were smoothly converted into the corresponding anti-Markovnikov alkenyl and alkyl boronate esters in high yields and high regio/stereoselectivity at room temperature and 50 ℃, respectively. The gram-scale hydroboration and further versatile conversions demonstrated great potential in the practical application. A plausible reaction mechanism was proposed based on the corresponding density function theory (DFT) calculations.

Key words: green chemistry, hydroboration, catalyst-free, alkyne, alkene

Cite this article

Kai Lu, Haoqi Qu, Xi Chen, Hui Qiu, Jing Zheng, Mengtao Ma. Catalyst-Free and Solvent-Free Hydroboration of Alkynes and Alkenes with Catecholborane[J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2197-2205.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 8

Scheme 1. Hydroboration of alkynes and alkenes with HBcat

Entry	n	Temp./℃	Time/h	Solvent	Conv.^a/%
1	1.1	r.t.	12	CDCl₃	70
2	1.2	r.t.	6		76
3	1.2	r.t.	12		99
4	1.2	r.t.	12	CDCl₃	99
5	1.2	40	6		80
6	1.2	40	12		99
7	3.0	r.t.	12		99
8	3.0	110	12	CDCl₃	99

Table 1. Optimization of reaction conditions for 4-ethynyl- toluene with HBcat

Table 2. Hydroboration of various alkynes with HBcata

Entry	n	Temp./℃	Time/h	Conv.^a/%
1	1.2	rt	12	12
2	1.2	50	12	76
3	1.2	50	20	81
4	1.5	50	20	99

Table 3. Optimization of reaction conditions for styrene with HBcat

Table 4. Hydroboration of various alkenes with HBcata

Scheme 2. (a) Scale-up hydroboration of phenylacetylene, (b) transformation of 1a to more stable 3a and (c) Suzuki-coupling reaction of 1a

Scheme 3. Proposed mechanism for the hydroboration of alkynes and alkenes

Figure 1. DFT calculations for the hydroboration of phenylacetylene (a, 298.15 K) and styrene (b, 323.15 K)

References 61

[1]	Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457. doi: 10.1021/cr00039a007
[2]	Dhillon, R. S. Hydroboration and Organic Synthesis, Springer Berlin Heidelberg, New York, 2007, pp. 59-99.
[3]	Saha, K.; Ghosh, S. Dalton Trans. 2022, 51, 2631. doi: 10.1039/D1DT04289K
[4]	Bose, S. K.; Mao, L. J.; Kuehn, L.; Radius, U.; Nekvinda, J.; Santos, W. L.; Westcott, S. A.; Steel, P. G.; Marder, T. B. Chem. Rev. 2021, 121, 13238. doi: 10.1021/acs.chemrev.1c00255
[5]	Luo, M.; Zang, S.; Yao, W.; Zheng, J.; Ma, M. Sci. Sin. Chim. 2020, 50, 639. doi: 10.1360/SSC-2020-0025
[6]	Shegavi, M. L.; Bose, S. K. Catal. Sci. Technol. 2019, 9, 3307. doi: 10.1039/C9CY00807A
[7]	Yoshida, H. ACS Catal. 2016, 6, 1799. doi: 10.1021/acscatal.5b02973
[8]	Geier, S. J.; Vogels, C. M.; Westcott, S. A. ACS Symp. Ser. 2016, 1236, 209.
[9]	Chong, C. C.; Kinjo, R. ACS Catal. 2015, 5, 3238. doi: 10.1021/acscatal.5b00428
[10]	Li, C.; Song, S.; Li, Y.; Xu, C.; Luo, Q.; Guo, Y.; Wang, X. Nat. Commun. 2021, 12, 3813. doi: 10.1038/s41467-021-24117-5
[11]	Cao, X.; Li, J.; Zhu, A.; Su, F.; Yao, W.; Xue, F.; Ma, M. Org. Chem. Front. 2020, 7, 3625. doi: 10.1039/D0QO00938E
[12]	Cao, X.; Wang, W.; Lu, K.; Yao, W.; Xue, F.; Ma, M. Dalton Trans. 2020, 49, 2776. doi: 10.1039/d0dt00465k pmid: 32073112
[13]	Wang, W.; Shen, X.; Zhao, F.; Jiang, H.; Yao, W.; Pullarkat, S. A.; Xu, L.; Ma, M. J. Org. Chem. 2018, 83, 69. doi: 10.1021/acs.joc.7b02076
[14]	Arase, A.; Nunokawa, Y.; Masuda, Y.; Hoshi, M. J. Chem. Soc., Chem. Commun. 1991, 205.
[15]	Kisan, S.; Krishnakumar, V.; Gunanathan, C. ACS Catal. 2017, 7, 5950. doi: 10.1021/acscatal.7b01750
[16]	MacNair, A. J.; Millet, C. R. P.; Nichol, G. S.; Ironmonger, A.; Thomas, S. P. ACS Catal. 2016, 6, 7217. doi: 10.1021/acscatal.6b02281
[17]	Ulm, F.; Cornaton, Y.; Djukic, J.; Chetcuti, M. J.; Ritleng, V. Chem.-Eur. J. 2020, 26, 8916. doi: 10.1002/chem.v26.41
[18]	Khalimon, A. Y.; Farha, P.; Kuzminab, L. G.; Nikonov, G. I. Chem. Commun. 2012, 48, 455. doi: 10.1039/C1CC14508H
[19]	Bai, Y.; Cui, C. Acta Chim. Sinica 2020, 78, 763. (in Chinese) doi: 10.6023/A20050163
	(白云平, 崔春明, 化学学报, 2020, 78, 763.) doi: 10.6023/A20050163
[20]	Hartwig, J. F.; Muhoro, C. N. Organometallics 2000, 19, 30. doi: 10.1021/om990507m
[21]	He, X.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 1696. doi: 10.1021/ja9516773
[22]	Gridnev, I. D.; Miyaura, N.; Suzuki, A. Organometallics 1993, 12, 589. doi: 10.1021/om00026a053
[23]	Leyva, A.; Zhang, X.; Corma, A. Chem. Commun. 2009, 33, 4947.
[24]	Yang, D.; Huang, X. Synth. Commun. 1996, 26, 4617. doi: 10.1080/00397919608004786
[25]	Ohmura, T.; Yamamoto, Y.; Miyaura, N. J. Am. Chem. Soc. 2000, 122, 4990. doi: 10.1021/ja0002823
[26]	Merola, J. S.; Knorr, J. R. J. Organomet. Chem. 2014, 750, 86. doi: 10.1016/j.jorganchem.2013.10.049
[27]	Mamidala, R.; Pandey, V. K.; Rit, A. Chem. Commun. 2019, 55, 989. doi: 10.1039/C8CC07499B
[28]	Arase, A.; Hoshi, M.; Mijin, A.; Nishi, K. Synth. Commun. 1995, 25, 1957. doi: 10.1080/00397919508015872
[29]	Shirakawa, K.; Arase, A.; Hoshi, M. Synthesis 2004, 1814.
[30]	Shao, H.; Chakrabarty, S.; Qi, X.; Takacs, J. M.; Liu, P. J. Am. Chem. Soc. 2021, 143, 4801. doi: 10.1021/jacs.1c01303
[31]	Xi, Y.; Su, B.; Qi, X.; Pedram, S.; Liu, P.; Hartwig, J. F. J. Am. Chem. Soc. 2020, 142, 18213. doi: 10.1021/jacs.0c08746
[32]	Bochat, A. J.; Shoba, V. M.; Takacs, J. M. Angew. Chem., Int. Ed. 2019, 58, 9434. doi: 10.1002/anie.v58.28
[33]	Rej, S.; Das, A.; Panda, T. K. Adv. Synth. Catal. 2021, 363, 4818. doi: 10.1002/adsc.v363.21
[34]	Ding, H.; Gao, W.; Yu, T.; Wang, Z.; Gou, F.; Ding, S. J. Org. Chem. 2022, 87, 1526. doi: 10.1021/acs.joc.1c02315
[35]	Zhong, M.; Gagne, Y.; Hope, T. O.; Pannecoucke, X.; Frenette, M.; Jubault, P.; Poisson, T. Angew. Chem., Int. Ed. 2021, 60, 14498. doi: 10.1002/anie.v60.26
[36]	Liu, J.; Xie, Y.; Wu, C.; Shao, Y.; Zhang, F.; Shi, Y.; Liu, Q.; Chen, J. Org. Chem. Front. 2021, 8, 3802. doi: 10.1039/D1QO00513H
[37]	Chen, J.; Shen, X.; Lu, Z. Angew. Chem., Int. Ed. 2021, 60, 690. doi: 10.1002/anie.v60.2
[38]	Kuciński, K.; Hreczycho, G. Green Chem. 2020, 22, 5210. doi: 10.1039/D0GC01430C
[39]	Harinath, A.; Bhattacharjee, J.; Panda, T. K. Chem. Commun. 2019, 55, 1386. doi: 10.1039/C8CC08841A
[40]	Wang, W.; Luo, M.; Zhu, D.; Yao, W.; Xu, L.; Ma, M. Org. Biomol. Chem. 2019, 17, 3604. doi: 10.1039/C9OB00485H
[41]	Jaladi, A. K.; Choi, H. S.; An, D. K. New J. Chem. 2020, 44, 13626. doi: 10.1039/D0NJ02612C
[42]	Yuan, K.; Suzuki, N.; Mellerup, S. K.; Wang, X.; Yamaguchi, S.; Wang, S. Org. Lett. 2016, 18, 720. doi: 10.1021/acs.orglett.5b03698
[43]	Stachowiak, H.; Kaźmierczak, J.; Kuciński, K.; Hreczycho, G. Green Chem. 2018, 20, 1738. doi: 10.1039/C8GC00042E
[44]	Wang, W.; Luo, M.; Yao, W.; Ma, M.; Pullarkat, S. A.; Xu, L.; Leung, P. New J. Chem. 2019, 43, 10744. doi: 10.1039/C9NJ02722J
[45]	Shimizu, K.; Yasutake, S.; Kondo, R. Chem. Pharm. Bull. 2003, 51, 318. doi: 10.1248/cpb.51.318
[46]	Segun, P. A.; Ogbole, O. O.; Akinleye, T. E.; Faleye, T. O. C.; Adeniji, A. J. Nat. Prod. Res. 2021, 35, 1909. doi: 10.1080/14786419.2019.1644505
[47]	Dery, S.; Alshanski, I.; Mervinetsky, E.; Feferman, D.; Yitzchaik, S.; Hurevich, M.; Gross, E. T. Chem. Commun. 2021, 57, 6233. doi: 10.1039/D1CC02491D
[48]	Zhang, M.; Xu, H. J. Comput. Chem. 2019, 40, 1772. doi: 10.1002/jcc.v40.19
[49]	Pandey, V. K.; Donthireddy, S. N. R.; Rit, A. Chem.-Asian J. 2019, 14, 3255. doi: 10.1002/asia.201901016
[50]	Geier, S. J.; Binder, J. F.; Vogels, C. M.; Watanabe, L. K.; Macdonald, C. L. B.; Westcott, S. A. New J. Chem. 2021, 45, 14908. doi: 10.1039/D1NJ01025E
[51]	Khalimon, A. Y.; Farhaa, P. M.; Nikonov, G. I. Dalton Trans. 2015, 44, 18945. doi: 10.1039/c5dt02945g pmid: 26469856
[52]	Farinola, G. M.; Fiandanese, V.; Mazzone, L.; Naso, F. Chem. Commun. 1995, 2523.
[53]	Garon, C. N.; McIsaac, D. I.; Vogels, C. M.; Decken, A.; Williams, I. D.; Kleeberg, C.; Marder, T. B.; Westcott, S. A. Dalton Trans. 2009, 9, 1624.
[54]	Li, S.; Li, J.; Xia, T.; Zhao, W. Chin. J. Chem. 2019, 37, 462. doi: 10.1002/cjoc.v37.5
[55]	Geier, M. J.; Geier, S. J.; Vogels, C. M.; Béland, F.; Westcott, S. A. Synlett 2009, 3, 477.
[56]	Morrill, C.; Grubbs, R. H. J. Org. Chem. 2003, 68, 6031. doi: 10.1021/jo0345345
[57]	Heard, D. M.; Tayler, E. R.; Cox, R. J.; Simpson, T. J.; Willis, C. L. Tetrahedron 2020, 76, 130717. doi: 10.1016/j.tet.2019.130717
[58]	Zhang, Y.; Zhao, X.; Bi, C.; Lu, W.; Song, M.; Wang, D.; Qing, G. Green Chem. 2021, 23, 1691. doi: 10.1039/D0GC03890C
[59]	Sun, B.; Zheng, S.; Mo, F. Chem. Commun. 2021, 57, 5674. doi: 10.1039/D1CC02134F
[60]	Wang, Z.; Wang, M.; Gao, J.; Shi, S.; Xu, Y. Org. Chem. Front. 2019, 6, 2949. doi: 10.1039/C9QO00750D
[61]	Wang, G.; Miao, T. Chem.-Eur. J. 2011, 17, 5787. doi: 10.1002/chem.v17.21

无催化剂、无溶剂条件下炔烃和烯烃与儿茶酚硼烷的硼氢化反应