碘介导下通过氧化性C—C键形成合成β-硝基胺与α-胺基腈类化合物

doi:10.6023/cjoc202305021

摘要/Abstract

以分子碘为单一氧化剂, 开发了一种无过渡金属催化的C—C键形成反应. 该反应可通过易得的叔胺分别与硝基烷、三甲基氰硅烷和亚磷酸酯合成β-硝基胺、α-胺基腈和α-胺基膦酸酯类化合物. 该合成方法具有操作简单, 底物适用范围广, 而且可以成功实现克级规模的合成.

关键词: 碘, C—C键形成, 叔胺, β-硝基胺, α-胺基腈

A transition-metal-free C—C bond formation reaction is developed employing molecular iodine as the sole oxidant to access β-nitroamines, α-aminonitriles and α-aminophosphonates from readily accessible tertiary amines with nitroalkanes, trimethylsilyl cyanide and phosphite, respectively. The present synthetic approach is operationally simple, has a broad substrate scope, and can be successfully conducted on a gram scale.

Key words: iodine, C—C bond formation, tertiary amine, β-nitroamine, α-aminonitrile

引用此文

李倩敏, 王漫漫, 于文全, 常俊标. 碘介导下通过氧化性C—C键形成合成β-硝基胺与α-胺基腈类化合物[J]. 有机化学, 2023, 43(11): 3966-3976.

Qianmin Li, Manman Wang, Wenquan Yu, Junbiao Chang. Synthesis of β-Nitroamines and α-Aminonitriles by I₂-Mediated Oxidative C—C Bond Formation[J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3966-3976.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 6

参考文献 36

[1]	(a) Tan, J.-P.; Li, X.; Chen, Y.; Rong, X.; Zhu, L.; Jiang, C.; Xiao, K.; Wang, T. Sci. China Chem. 2020, 63, 1091. doi: 10.1007/s11426-020-9754-7
	(b) El Sayed, M. T.; Sarhan, A. E.; Ahmed, E.; Khattab, R. R.; Elnaggar, M.; El-Messery, S. M.; Shaldam, M. A.; Hassan, G. S. ChemistrySelect 2020, 5, 3445. doi: 10.1002/slct.v5.11
[2]	(a) Méndez-Álvarez, E.; Soto-Otero, R.; Sánchez-Sellero, I.; Lamas, M. L.-R. Life Sci. 1997, 60, 1719. doi: 10.1016/s0024-3205(97)00114-8 pmid: 24936707
	(b) Deng, X.; Lin, F.; Zhang, Y.; Li, Y.; Zhou, L.; Lou, B.; Li, Y.; Dong, J.; Ding, T.; Jiang, X.; Wang, R.; Ye, D. Eur. J. Med. Chem. 2014, 73, 1. doi: 10.1016/j.ejmech.2013.12.002 pmid: 24936707
	(c) Yang, R.; Ruan, Q.; Zhang, B.-Y.; Zheng, Z.-L.; Miao, F.; Zhou, L.; Geng, H.-L. Molecules 2014, 19, 8051. doi: 10.3390/molecules19068051 pmid: 24936707
	(d) Cao, F.-J.; Xu, M.-X.; Zhou, B.-H.; Du, Y.-S.; Yao, J.-H.; Zhou, L. Toxicol. In Vitro 2019, 54, 295. doi: 10.1016/j.tiv.2018.10.007 pmid: 24936707
	(e) Gajic, M.; Ilic, B. S.; Bondzic, B. P.; Dzambaski, Z.; Kojic, V. V.; Jakimov, D. S.; Kocic, G.; Smelcerovic, A. Chem. Biodiversity 2021, 18, e2100261. doi: 10.1002/cbdv.v18.8 pmid: 24936707
[3]	Pabuççuoglu, V.; Arar, G.; Gözler, T.; Freyer, A. J.; Shamma, M. J. Nat. Prod. 1989, 52, 716. doi: 10.1021/np50064a008
[4]	Romo-Pérez, A.; Miranda, L. D.; Chávez-Blanco, A. D.; Dueñas- González, A.; Camacho-Corona, M. d. R.; Acosta-Huerta, A.; García, A. Eur. J. Med. Chem. 2017, 138, 1. doi: S0223-5234(17)30467-1 pmid: 28641156
[5]	Hayashi, K.; Minoda, K.; Nagaoka, Y.; Hayashi, T.; Uesato, S. Bioorg. Med. Chem. Lett. 2007, 17, 1562. doi: 10.1016/j.bmcl.2006.12.085 pmid: 17239594
[6]	Cao, F.-J.; Yang, R.; Lv, C.; Ma, Q.; Lei, M.; Geng, H.-L.; Zhou, L. Eur. J. Pharm. Sci. 2015, 67, 45. doi: 10.1016/j.ejps.2014.10.020
[7]	(a) Dyker, G. Angew. Chem. Int. Ed. 1997, 36, 1700. doi: 10.1002/anie.v36:16 pmid: 15527316
	(b) Ballini, R.; Petrini, M. Tetrahedron 2004, 60, 1017. doi: 10.1016/j.tet.2003.11.016 pmid: 15527316
	(c) Bernardi, L.; Bonini, B. F.; Capitó, E.; Dessole, G.; Comes-Franchini, M.; Fochi, M.; Ricci, A. J. Org. Chem. 2004, 69, 8168. pmid: 15527316
	(d) Murahashi, S.-I.; Zhang, D. Chem. Soc. Rev. 2008, 37, 1490. doi: 10.1039/b706709g pmid: 15527316
[8]	(a) Tsang, A. S.-K.; Todd, M. H. Tetrahedron Lett. 2009, 50, 1199.
	(b) Nobuta, T.; Fujiya, A.; Yamaguchi, T.; Tada, N.; Miura, T.; Itoh, A. RSC Adv. 2013, 3, 10189. doi: 10.1039/c3ra41850b
	(c) Liu, P.-Y.; Zhang, C.; Zhao, S.-C.; Yu, F.; Li, F.; He, Y.-P. J. Org. Chem. 2017, 82, 12786. doi: 10.1021/acs.joc.7b02021
	(d) Zhang, R.; Qin, Y.; Zhang, L.; Luo, S. J. Org. Chem. 2019, 84, 2542. doi: 10.1021/acs.joc.8b02948
[9]	(a) Chu, L.; Qing, F.-L. Chem. Commun. 2010, 46, 6285. doi: 10.1039/c0cc01073a
	(b) Zhang, Y.; Peng, H.; Zhang, M.; Cheng, Y.; Zhu, C. Chem. Commun. 2011, 47, 2354. doi: 10.1039/C0CC03844J
	(c) Kumar, R. A.; Saidulu, G.; Prasad, K. R.; Kumar, G. S.; Sridhar, B.; Reddy, K. R. Adv. Synth. Catal. 2012, 354, 2985. doi: 10.1002/adsc.v354.16
	(d) Nobuta, T.; Tada, N.; Fujiya, A.; Kariya, A.; Miura, T.; Itoh, A. Org. Lett. 2013, 15, 574. doi: 10.1021/ol303389t
	(e) Zhu, S.-L.; Ou, S.; Zhao, M.; Shen, H.; Wu, C.-D. Dalton Trans. 2015, 44, 2038. doi: 10.1039/C4DT03371J
	(f) Liang, W.; Zhang, T.; Liu, Y.; Huang, Y.; Liu, Z.; Liu, Y.; Yang, B.; Zhou, X.; Zhang, J. ChemSusChem 2018, 11, 3586. doi: 10.1002/cssc.v11.20
[10]	(a) Condie, A. G.; González-Gómez, J. C.; Stephenson, C. R. J. J. Am. Chem. Soc. 2010, 132, 1464. doi: 10.1021/ja909145y pmid: 34123323
	(b) Rueping, M.; Zhu, S.; Koenigs, R. M. Chem. Commun. 2011, 12709. pmid: 34123323
	(c) Gandy, M. N.; Raston, C. L.; Stubbs, K. A. Chem. Commun. 2015, 51, 11041. doi: 10.1039/C5CC02153G pmid: 34123323
	(d) Wang, X.-Z.; Meng, Q.-Y.; Zhong, J.-J.; Gao, X.-W.; Lei, T.; Zhao, L.-M.; Li, Z.-J.; Chen, B.; Tung, C.-H.; Wu, L.-Z. Chem. Commun. 2015, 51, 11256. doi: 10.1039/C5CC03421C pmid: 34123323
	(e) Li, X.; Li, Y.; Huang, Y.; Zhang, T.; Liu, Y.; Yang, B.; He, C.; Zhou, X.; Zhang, J. Green Chem. 2017, 19, 2925. doi: 10.1039/C6GC03558B pmid: 34123323
	(f) Chen, K.; Cheng, Y.; Chang, Y.; Li, E.; Xu, Q.-L.; Zhang, C.; Wen, X.; Sun, H. Tetrahedron 2018, 74, 483. doi: 10.1016/j.tet.2017.12.019 pmid: 34123323
	(g) Ide, T.; Shimizu, K.; Egami, H.; Hamashima, Y. Tetrahedron Lett. 2018, 59, 3258. doi: 10.1016/j.tetlet.2018.07.030 pmid: 34123323
	(h) Kosso, A. R. O.; Sellet, N.; Baralle, A.; Cormier, M.; Goddard, J.-P. Chem. Sci. 2021, 12, 6964. doi: 10.1039/d1sc00998b pmid: 34123323
	(i) Lin, C.; Li, P.; Wang, L. Tetrahedron Lett. 2021, 73, 153102. doi: 10.1016/j.tetlet.2021.153102 pmid: 34123323
[11]	(a) Baslé, O.; Li, C.-J. Green Chem. 2007, 9, 1047. doi: 10.1039/b707745a
	(b) Murahashi, S.-I.; Nakae, T.; Terai, H.; Komiya, N. J. Am. Chem. Soc. 2008, 130, 11005. doi: 10.1021/ja8017362
	(c) Alagiri, K.; Prabhu, K. R. Org. Biomol. Chem. 2012, 10, 835. doi: 10.1039/C1OB06466E
	(d) Meng, Q.-Y.; Liu, Q.; Zhong, J.-J.; Zhang, H.-H.; Li, Z.-J.; Chen, B.; Tung, C.-H.; Wu, L.-Z. Org. Lett. 2012, 14, 5992. doi: 10.1021/ol3028785
	(e) Brzozowski, M.; Forni, J. A.; Savage, G. P.; Polyzos, A. Chem. Commun. 2015, 51, 334. doi: 10.1039/C4CC07913B
	(f) Patil, M. R.; Dedhia, N. P.; Kapdi, A. R.; Kumar, A. V. J. Org. Chem. 2018, 83, 4477. doi: 10.1021/acs.joc.8b00203
	(g) Wang, H.; Wang, A.; Xia, Z.; Zhou, W.; Sun, Z.; Qian, J.; He, M. Chin. J. Org. Chem. 2020, 40, 2099. (in Chinese) doi: 10.6023/cjoc202004028
	(王慧, 王安玮, 夏珍珍, 周维友, 孙中华, 钱俊峰, 何明阳, 有机化学, 2020, 40, 2099.) doi: 10.6023/cjoc202004028
	(h) Bjerg, E. E.; Marchan-Garcia, J.; Buxaderas, E.; Moglie, Y.; Radivoy, G. J. Org. Chem. 2022, 87, 13480. doi: 10.1021/acs.joc.2c01782
[12]	Tanoue, A.; Yoo, W.-J.; Kobayashi, S. Org. Lett. 2014, 16, 2346. doi: 10.1021/ol500661t pmid: 24725125
[13]	Dhineshkumar, J.; Lamani, M.; Alagiri, K.; Prabhu, K. R. Org. Lett. 2013, 15, 1092. doi: 10.1021/ol4001153 pmid: 23419035
[14]	(a) Liu, J.; Wei, W.; Zhao, T.; Liu, X.; Wu, J.; Yu, W.; Chang, J. J. Org. Chem. 2016, 81, 9326. doi: 10.1021/acs.joc.6b01960
	(b) Lv, Z.; Wang, B.; Hu, Z.; Zhou, Y.; Yu, W.; Chang, J. J. Org. Chem. 2016, 81, 9924. doi: 10.1021/acs.joc.6b02100
[15]	(a) Yi, X.; Zhao, Z.; Wang, M.; Yu, W.; Chang, J. Org. Lett. 2022, 24, 8703. doi: 10.1021/acs.orglett.2c03630
	(b) Wang, M.; Ye, W.; Sun, N.; Yu, W.; Chang, J. J. Org. Chem. 2023, 88, 1061. doi: 10.1021/acs.joc.2c02509
[16]	(a) Jayram, J.; Xulu, B. A.; Jeena, V. Tetrahedron 2019, 75, 130617. doi: 10.1016/j.tet.2019.130617
	(b) Huang, H.-Y.; Wu, H.-R.; Wei, F.; Wang, D.; Liu, L. Org. Lett. 2015, 17, 3702. doi: 10.1021/acs.orglett.5b01662
	(c) Gromada, J.; Matyjaszewski, K. Macromolecules 2001, 34, 7664. doi: 10.1021/ma010864k
	(d) Wan, J.-P.; Zhong, S.; Guo, Y.; Wei, L. Eur. J. Org. Chem. 2017, 440.
[17]	Tran, V. H.; La, M. T.; Kim, H.-K. Tetrahedron Lett. 2019, 60, 1860. doi: 10.1016/j.tetlet.2019.06.019
[18]	Yan, C.; Liu, Y.; Wang, Q. RSC Adv. 2014, 4, 60075. doi: 10.1039/C4RA12922A
[19]	Zhang, L.; Peng, C.; Zhao, D.; Wang, Y.; Fu, H.-J.; Shen, Q.; Li, J.-X. Chem. Commun. 2012, 48, 5928. doi: 10.1039/c2cc32009f
[20]	Huang, B.-Q.; Chen, Y.; Zhang, X.-J.; Yan, M. Eur. J. Org. Chem. 2021, 3015.
[21]	Tian, H.; Xu, W.; Liu, Y.; Wang, Q. Chem. Commun. 2019, 55, 14813. doi: 10.1039/C9CC08056B
[22]	Qian, W.; Zhou, X. Chinese J. Org. Chem. 2013, 33, 2430. doi: 10.6023/cjoc201305052
[23]	Tran, V. H.; La, M. T.; Kang, S.; Kim, H.-K. Org. Biomol. Chem. 2020, 18, 5008. doi: 10.1039/D0OB00880J
[24]	Matsuda, N.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem. Int. Ed. 2012, 124, 3702. doi: 10.1002/ange.v124.15
[25]	Zhou, J.; Li, L.; Wang, S.; Yan, M.; Wei, W. Green Chem. 2020, 22, 3421. doi: 10.1039/D0GC01256D
[26]	Tsang, A. S.-K.; Hashmi, A. S. K.; Comba, P.; Kerscher, M.; Chan, B.; Todd, M. H. Chem.-Eur. J. 2017, 23, 9313. doi: 10.1002/chem.v23.39
[27]	Kim, H.-K.; Lee, A. Tetrahedron Lett. 2016, 57, 4890. doi: 10.1016/j.tetlet.2016.09.038
[28]	Casarini, D.; Davalli, S.; Lunazzi, L. J. Org. Chem. 1989, 54, 4616. doi: 10.1021/jo00280a031
[29]	Shu, X.-Z.; Xia, X.-F.; Yang, Y.-F.; Ji, K.-G.; Liu, X.-Y.; Liang, Y.-M. J. Org. Chem. 2009, 74, 7464. doi: 10.1021/jo901583r
[30]	Zhu, S.-S.; Liu, Y.; Chen, X.-L.; Qu, L.-B.; Yu, B. ACS Catal. 2022, 12, 126. doi: 10.1021/acscatal.1c03765
[31]	Yu, J.; Wang, Z.; Zhang, Y.; Su, W. Tetrahedron 2015, 71, 6116. doi: 10.1016/j.tet.2015.06.105
[32]	Zhang, G.; Ma, Y.; Cheng, G.; Liu, D.; Wang, R. Org. Lett. 2014, 16, 656. doi: 10.1021/ol500045p pmid: 24479944
[33]	Wang, J.-H.; Li, X.-B.; Li, J.; Lei, T.; Wu, H.-L.; Nan, X.-L.; Tung, C.-H.; Wu, L.-Z. Chem. Commun. 2019, 55, 10376. doi: 10.1039/C9CC05375A
[34]	Liu, L.; Wang, Z.; Fu, X.; Yan, C.-H. Org. Lett. 2012, 14, 5692. doi: 10.1021/ol302708r
[35]	Xia, Q.; Zhang, W.; Li, Y.; Cheng, L.; Liang, X.; Dai, P. CN 112390696B, 2021.
[36]	Mudithanapelli, C.; Dhorma, L. P.; Kim, M.-H. Org. Lett. 2019, 21, 3098. doi: 10.1021/acs.orglett.9b00751 pmid: 30986072

Entry	2a/equiv.	Base	Solvent	Temp.	t/h	Yield^b/%
1	2	NaOAc	DCE	Reflux	1	Trace
2	2	NaOAc	Toluene	Reflux	1	Trace
3	2	NaOAc	DMSO	100 °C	1	34
4	2	NaOAc	ⁱPrOH	Reflux	2	59
5	2	NaOAc	MeCN	Reflux	5.5	61
6	2	NaOAc	THF	Reflux	11	58
7	2	NaOAc	1,4-Dioxane	Reflux	1	84
8	2	NaOAc	1,4-Dioxane	80 °C	1.5	32
9	1.5	NaOAc	1,4-Dioxane	Reflux	1	72
10	2.5	NaOAc	1,4-Dioxane	Reflux	1	92
11	3	NaOAc	1,4-Dioxane	Reflux	1	87
12	2.5	NaHCO₃	1,4-Dioxane	Reflux	4	19
13	2.5	Na₂CO₃	1,4-Dioxane	Reflux	4.5	74
14	2.5	K₂CO₃	1,4-Dioxane	Reflux	1	32
15	2.5	K₃PO₄	1,4-Dioxane	Reflux	0.5	49
16	2.5	NaOH	1,4-Dioxane	Reflux	1.5	77
17	2.5	KO^tBu	1,4-Dioxane	Reflux	0.5	59
18	2.5	DBU	1,4-Dioxane	Reflux	5	Trace
19	2.5	NEt₃	1,4-Dioxane	Reflux	5	Trace
20^c	2.5	NaOAc	1,4-Dioxane	Reflux	1.5	89
21^d	2.5	NaOAc	1,4-Dioxane	Reflux	0.5	49
22^e	2.5	NaOAc	1,4-Dioxane	Reflux	0.5	74

Entry	2a/equiv.	Base	Solvent	Temp.	t/h	Yield^b/%
1	2	NaOAc	DCE	Reflux	1	Trace
2	2	NaOAc	Toluene	Reflux	1	Trace
3	2	NaOAc	DMSO	100 °C	1	34
4	2	NaOAc	ⁱPrOH	Reflux	2	59
5	2	NaOAc	MeCN	Reflux	5.5	61
6	2	NaOAc	THF	Reflux	11	58
7	2	NaOAc	1,4-Dioxane	Reflux	1	84
8	2	NaOAc	1,4-Dioxane	80 °C	1.5	32
9	1.5	NaOAc	1,4-Dioxane	Reflux	1	72
10	2.5	NaOAc	1,4-Dioxane	Reflux	1	92
11	3	NaOAc	1,4-Dioxane	Reflux	1	87
12	2.5	NaHCO₃	1,4-Dioxane	Reflux	4	19
13	2.5	Na₂CO₃	1,4-Dioxane	Reflux	4.5	74
14	2.5	K₂CO₃	1,4-Dioxane	Reflux	1	32
15	2.5	K₃PO₄	1,4-Dioxane	Reflux	0.5	49
16	2.5	NaOH	1,4-Dioxane	Reflux	1.5	77
17	2.5	KO^tBu	1,4-Dioxane	Reflux	0.5	59
18	2.5	DBU	1,4-Dioxane	Reflux	5	Trace
19	2.5	NEt₃	1,4-Dioxane	Reflux	5	Trace
20^c	2.5	NaOAc	1,4-Dioxane	Reflux	1.5	89
21^d	2.5	NaOAc	1,4-Dioxane	Reflux	0.5	49
22^e	2.5	NaOAc	1,4-Dioxane	Reflux	0.5	74

Entry	I₂/equiv.	Base	Solvent	Temp.	t/h	Yield^b/%
1	2	NaOAc	1,4-Dioxane	Reflux	2.5	44
2	2	NaOAc	DMSO	100 °C	4	41
3	2	NaOAc	MeCN	Reflux	4	58
4	2	NaOAc	Toluene	Reflux	0.5	68
5	2	NaOAc	DCE	Reflux	1	72
6	3	NaOAc	DCE/MeCN (V:V=1:1)	Reflux	4	88
7	3	NaOAc	DCE/MeCN (V:V=2:1)	Reflux	2	90
8	3	NaOAc	DCE/MeCN (V:V=3:1)	Reflux	1.5	77
9	3	NaHCO₃	DCE/MeCN (V:V=2:1)	Reflux	2.5	82
10	3	Na₂CO₃	DCE/MeCN (V:V=2:1)	Reflux	3.5	46
11	3	NaOH	DCE/MeCN (V:V=2:1)	Reflux	4	65
12	3	NaOAc	DCE/MeCN (V:V=2:1)	60 °C	14	78
13	4	NaOAc	DCE/MeCN (V:V=2:1)	Reflux	0.5	92

Entry	I₂/equiv.	Base	Solvent	Temp.	t/h	Yield^b/%
1	2	NaOAc	1,4-Dioxane	Reflux	2.5	44
2	2	NaOAc	DMSO	100 °C	4	41
3	2	NaOAc	MeCN	Reflux	4	58
4	2	NaOAc	Toluene	Reflux	0.5	68
5	2	NaOAc	DCE	Reflux	1	72
6	3	NaOAc	DCE/MeCN (V:V=1:1)	Reflux	4	88
7	3	NaOAc	DCE/MeCN (V:V=2:1)	Reflux	2	90
8	3	NaOAc	DCE/MeCN (V:V=3:1)	Reflux	1.5	77
9	3	NaHCO₃	DCE/MeCN (V:V=2:1)	Reflux	2.5	82
10	3	Na₂CO₃	DCE/MeCN (V:V=2:1)	Reflux	3.5	46
11	3	NaOH	DCE/MeCN (V:V=2:1)	Reflux	4	65
12	3	NaOAc	DCE/MeCN (V:V=2:1)	60 °C	14	78
13	4	NaOAc	DCE/MeCN (V:V=2:1)	Reflux	0.5	92