4-Dimethylaminopyridine-Boryl Radical Promoted Regioselective Radical Hydroboration of Electron-Deficient Alkenes

doi:10.6023/cjoc202103041

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (5): 1957-1967.DOI: 10.6023/cjoc202103041 Previous Articles Next Articles

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4-二甲胺基吡啶-硼自由基促进的缺电子烯烃区域选择性硼氢化反应

黄云帅¹, 靳小慧¹, 张凤莲¹^,^*(), 汪义丰¹^,^*()

1 中国科学技术大学化学系合肥 230026

收稿日期:2021-03-23 修回日期:2021-04-09 发布日期:2021-04-25
通讯作者: 张凤莲, 汪义丰
基金资助:
国家自然科学基金(21971226); 中央高校基本科研业务费专项资金(WK2060000017)

4-Dimethylaminopyridine-Boryl Radical Promoted Regioselective Radical Hydroboration of Electron-Deficient Alkenes

Yunshuai Huang¹, Xiaohui Jin¹, Fenglian Zhang¹^,^*(), Yifeng Wang¹^,^*()

1 Department of Chemistry, University of Science and Technology of China, Hefei 230026

Received:2021-03-23 Revised:2021-04-09 Published:2021-04-25
Contact: Fenglian Zhang, Yifeng Wang
About author:
* Corresponding authors. E-mail: zfl9@ustc.edu.cn;
E-mail: yfwangzj@ustc.edu.cn
Supported by:
National Natural Science Foundation of China(21971226); Fundamental Research Funds for the Central Universities(WK2060000017)

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Abstract

Organoboron compounds have shown significant applications in modern chemical synthesis. Hydroboration of alkenes is among the most widely used methods to access these targets. Herein, a regioselective radical hydroboration reaction of electron-deficient alkenes with 4-dimethylaminopyridine (DMAP)-boryl radical for the synthesis of α-boryl functionalized molecules is reported. The reaction features specific α-regioselectivity, mild reaction conditions, good functional group tolerance, and broad substrate scope. α,β-Unsaturated esters, amides, carboxylic acid, nitrile, trifluoromethyl molecule, sulfone, and phosphonate are viable substrates for this reaction. The resulting α-boryl functionalized molecules can be further transformed to various useful building blocks.

Key words: 4-dimethylaminopyridine-boryl radical, electron-deficient alkenes, regioselectivity, hydroboration, radical chemistry

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Yunshuai Huang, Xiaohui Jin, Fenglian Zhang, Yifeng Wang. 4-Dimethylaminopyridine-Boryl Radical Promoted Regioselective Radical Hydroboration of Electron-Deficient Alkenes[J]. Chinese Journal of Organic Chemistry, 2021, 41(5): 1957-1967.

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References 19

[1]	Hall, D. G. Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials, 2nd ed., Wiley-VCH, Weinheim, Germany, 2011.
[2]	(a) Lei, Z.; Huang, Z. Synlett 2013, 24, 1745. doi: 10.1055/s-00000083
	(b) Beletskaya, I.; Pelter, A. Tetrahedron 1997, 53, 4957. doi: 10.1016/S0040-4020(97)00001-X
	(c) Burgess, K.; Ohlmeyer, M. J. Chem. Rev. 1991, 91, 1179. doi: 10.1021/cr00006a003
	(d) Chen, J.-B.; Whiting, A. Synthesis 2018, 50, 3843. doi: 10.1055/s-0037-1609583
[3]	(a) Schiffner, J. A.; Müther, K.; Oestreich, M. Angew. Chem., Int. Ed. 2010, 49, 1194. doi: 10.1002/anie.200906521
	(b) Mantilli, L.; Mazet, C. ChemCatChem 2010, 2, 501. doi: 10.1002/cctc.201000008
	(c) Calow, A. D. J.; Whiting, A. Org. Biomol. Chem. 2012, 10, 5485. doi: 10.1039/c2ob25908g
	(d) Stavber, G.; Časar, Z. ChemCatChem 2014, 6, 2162. doi: 10.1002/cctc.201402176
	(e) Lee, S.; Yun, J. In Synthesis and Application of Organoboron Compounds, Vol. 49, Eds.: Fernandez, E.; Whiting, A., 2015, pp.73~92.
	(f) Collins, B. S. L.; Wilson, C. M.; Myers, E. L.; Aggarwal, V. K. Angew. Chem., Int. Ed. 2017, 56, 11700. doi: 10.1002/anie.201701963
	(g) Liu, Y.; Zhang, W. Chin. J. Org. Chem. 2016, 36, 2249. (in Chinese). doi: 10.6023/cjoc201609005
	(刘媛媛, 张万斌, 有机化学, 2016, 36, 2249.) doi: 10.6023/cjoc201609005
[4]	Ibrahim, M. R.; Bühl, M.; Knab, R.; Schleyer, P. V. R. J. Comput. Chem. 1992, 13, 423. doi: 10.1002/jcc.v13:4
[5]	(a) He, Z.; Zajdlik, A.; Yudin, A. K. Acc. Chem. Res. 2014, 47, 1029. doi: 10.1021/ar400210c
	(b) He, Z.; Zajdlik, A.; Yudin, A. K. Dalton Trans. 2014, 43, 11434. doi: 10.1039/C4DT00817K
[6]	Sucrow, W.; Zühlke, L.; Slopianka, M.; Pickardt, J. Chem. Ber. 1977, 110, 2818. doi: 10.1002/(ISSN)1099-0682
[7]	Ng, E. W. H.; Low, K.-H.; Chiu, P. J. Am. Chem. Soc. 2018, 140, 3537. doi: 10.1021/jacs.8b00614
[8]	Radcliffe, J. E.; Fasano, V.; Adams, R. W.; You, P.; Ingleson, M. J. Chem. Sci. 2019, 10, 1434. doi: 10.1039/c8sc04305a pmid: 30809360
[9]	(a) Jin, J.; Xia, H.; Zhang, F.; Wang, Y. Chin. J. Org. Chem. 2020, 40, 2185. (in Chinese). doi: 10.6023/cjoc202005017
	(靳继康, 夏慧敏, 张凤莲, 汪义丰, 有机化学, 2020, 40, 2185.) doi: 10.6023/cjoc202005017
	(b) Zhang, F.-L.; Wang, Y.-F. In Science of Synthesis : Advances in Organoboron Chemistry towards Organic Synthesis, Ed.: Fernández, E., Thieme, Stuttgart, 2019, pp.355~392.
	(c) Taniguchi, T. Eur. J. Org. Chem. 2019, 2019, 6308. doi: 10.1002/ejoc.201901010
	(d) Yang, J.; Li, Z.; Zhu, S. Chin. J. Org. Chem. 2017, 37, 2481. (in Chinese).
	(杨吉民, 李子奇, 朱守非, 有机化学, 2017, 37, 2481.) doi: 10.6023/cjoc201705034
	(e) Xu, A.-Q.; Zhang, F.-L.; Ye, T.; Yu, Z.-X.; Wang, Y.-F. CCS Chem. 2019, 1, 504. doi: 10.31635/ccschem.019.20190025
	(f) Ueng, S.-H.; Makhlouf Brahmi, M.; Derat, É.; Fensterbank, L.; Lacôte, E.; Malacria, M.; Curran, D. P. J. Am. Chem. Soc. 2008, 130, 10082. doi: 10.1021/ja804150k
[10]	(a) Ren, S.-C.; Zhang, F.-L.; Qi, J.; Huang, Y.-S.; Xu, A.-Q.; Yan, H.-Y.; Wang, Y.-F. J. Am. Chem. Soc. 2017, 139, 6050. doi: 10.1021/jacs.7b01889
	(b) Watanabe, T.; Hirose, D.; Curran, D. P.; Taniguchi, T. Chem. Eur. J. 2017, 23, 5404. doi: 10.1002/chem.v23.23
	(c) Zhou, N.; Yuan, X.-A.; Zhao, Y.; Xie, J.; Zhu, C. Angew. Chem., Int. Ed. 2018, 57, 3990. doi: 10.1002/anie.201800421
	(d) Dai, W.; Geib, S. J.; Curran, D. P. J. Am. Chem. Soc. 2019, 141, 12355. doi: 10.1021/jacs.9b05547
	(e) Qi, J.; Zhang, F.-L.; Jin, J.-K.; Zhao, Q.; Li, B.; Liu, L.-X.; Wang, Y.-F. Angew. Chem., Int. Ed. 2020, 59, 12876. doi: 10.1002/anie.v59.31
	(f) Xia, P. J.; Song, D.; Ye, Z. P.; Hu, Y. Z.; Xiao, J. A.; Xiang, H. Y.; Chen, X. Q.; Yang, H. Angew. Chem., Int. Ed. 2020, 59, 6706. doi: 10.1002/anie.v59.17
	(g) Zhu, C.; Dong, J.; Liu, X.; Gao, L.; Zhao, Y.; Xie, J.; Li, S.; Zhu, C. Angew. Chem., Int. Ed. 2020, 59, 12817. doi: 10.1002/anie.v59.31
	(h) Xu, W.; Jiang, H.; Leng, J.; Ong, H. W.; Wu, J. Angew. Chem., Int. Ed. 2020, 59, 4009. doi: 10.1002/anie.v59.10
	(i) Dai, W.; Geib, S. J.; Curran, D. P. J. Am. Chem. Soc. 2020, 142, 6261. doi: 10.1021/jacs.0c00490
	(j) Kawamoto, T.; Morioka, T.; Noguchi, K.; Curran, D. P.; Kamimura, A. Org. Lett. 2021, 23, 1825. doi: 10.1021/acs.orglett.1c00230
	(k) Liu, Y.; Li, J.-L.; Liu, X.-G.; Wu, J.-Q.; Huang, Z.-S.; Li, Q.; Wang, H. Org. Lett. 2021, 23, 1891. doi: 10.1021/acs.orglett.1c00309
	Xu, H.; Jiang, Z. Chin. J. Org. Chem. 2020, 40, 3483. (in Chinese). doi: 10.6023/cjoc202000069
	(许荷欢, 江智勇, 有机化学, 2020, 40, 3483.) doi: 10.6023/cjoc202000069
[11]	(a) Ren, S.-C.; Zhang, F.-L.; Xu, A.-Q.; Yang, Y.; Zheng, M.; Zhou, X.; Fu, Y.; Wang, Y.-F. Nat. Commun. 2019, 10, 1934. doi: 10.1038/s41467-019-09825-3
	(b) Huang, Y.-S.; Wang, J.; Zheng, W.-X.; Zhang, F.-L.; Yu, Y.-J.; Zheng, M.; Zhou, X.; Wang, Y.-F. Chem. Commun. 2019, 55, 11904. doi: 10.1039/C9CC06506G
[12]	Brahmi, M. M.; Monot, J.; Desage-El Murr, M.; Curran, D. P.; Fensterbank, L.; Lacôte, E.; Malacria, M. J. Org. Chem. 2010, 75, 6983. doi: 10.1021/jo101301d
[13]	(a) Lalevée, J.; Blanchard, N.; Tehfe, M.-A.; Chany, A.-C.; Fouassier, J.-P. Chem.-Eur. J. 2010, 16, 12920. doi: 10.1002/chem.v16.43
	(b) Lalevée, J.; Blanchard, N.; Chany, A.-C.; Tehfe, M.-A.; Allonas, X.; Fouassier, J.-P. J. Phys. Org. Chem. 2009, 22, 986. doi: 10.1002/poc.v22:10
	(c) Jin, J.-K.; Zhang, F.-L.; Wang, Y.-F. Acta Chim. Sinica 2019, 77, 889. (in Chinese). doi: 10.6023/A19050173
	(靳继康, 张凤莲, 汪义丰, 化学学报, 2019, 77, 889.) doi: 10.6023/A19050173
[14]	Yu, Y.-J.; Zhang, F.-L.; Peng, T.-Y.; Wang, C.-L.; Cheng, J.; Chen, C.; Houk, K. N.; Wang, Y.-F. Science 2021, 371, 1232. doi: 10.1126/science.abg0781
[15]	(a) Roberts, B. P. Chem. Soc. Rev. 1999, 28, 25. doi: 10.1039/a804291h
	(b) Pan, X.; Lacôte, E.; Lalevée, J.; Curran, D. P. J. Am. Chem. Soc. 2012, 134, 5669. doi: 10.1021/ja300416f
[16]	Staubitz, A.; Robertson, A. P. M.; Sloan, M. E.; Manners, I. Chem. Rev. 2010, 110, 4023. doi: 10.1021/cr100105a
[17]	(a) Griller, D.; Ingold, K. U. Acc. Chem. Res. 1980, 13, 317. doi: 10.1021/ar50153a004
	(b) Newcomb, M. Tetrahedron 1993, 49, 1151. doi: 10.1016/S0040-4020(01)85808-7
[18]	Dénès, F.; Pichowicz, M.; Povie, G.; Renaud, P. Chem. Rev. 2014, 114, 2587. doi: 10.1021/cr400441m
[19]	(a) Bonet, A.; Odachowski, M.; Leonori, D.; Essafi, S.; Aggarwal, V. K. Nat. Chem. 2014, 6, 584. doi: 10.1038/nchem.1971
	(b) Llaveria, J.; Leonori, D.; Aggarwal, V. K. J. Am. Chem. Soc. 2015, 137, 10958. doi: 10.1021/jacs.5b07842

Entry	PhSH (x mol%)	Initiator	Conditions	Yield^b/% of 3aa
1	50	AIBN	80 ℃, 9 h	46
2	50	ACCN	95 ℃, 9 h	55
3	50	ABVN	60 ℃, 4 h	69
4	50	TBHN	60 ℃, 4 h	83
5	50	Et₃B	Air, r.t., 9 h	85^c
6	20	Et₃B	Air, r.t., 9 h	84^c
7	20	—	O₂, r.t., 9 h	0 (>95)^d
8^e	20	Et₃B	Air, r.t., 9 h	0 (>95)^d

Entry	PhSH (x mol%)	Initiator	Conditions	Yield^b/% of 3aa
1	50	AIBN	80 ℃, 9 h	46
2	50	ACCN	95 ℃, 9 h	55
3	50	ABVN	60 ℃, 4 h	69
4	50	TBHN	60 ℃, 4 h	83
5	50	Et₃B	Air, r.t., 9 h	85^c
6	20	Et₃B	Air, r.t., 9 h	84^c
7	20	—	O₂, r.t., 9 h	0 (>95)^d
8^e	20	Et₃B	Air, r.t., 9 h	0 (>95)^d

4-二甲胺基吡啶-硼自由基促进的缺电子烯烃区域选择性硼氢化反应

4-Dimethylaminopyridine-Boryl Radical Promoted Regioselective Radical Hydroboration of Electron-Deficient Alkenes

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