Iridium Catalyzed C—H Amidation of Benzamides with Phosphoryl Azides in Ionic Liquids

doi:10.6023/cjoc202104039

Abstract

Phosphoramides are common structures in natural products and bioactive molecules. Additionally, they are also important intermediates in synthetic chemistry. In this paper, a direct, simple, efficient and relatively greener transition metal iridium catalyzed C—H bond amidation was reported. The target conversion was achieved in ionic liquids using weakly coordinated benzamides and phosphoryl azides as substrates and amidation reagents, respectively. Moderate to excellent isolated yields were obtained, showing good functional group tolerance and high regioselectivity. Furthermore, a possible mechanism of the reaction was proposed. The establishment of the catalytic system enriches the synthesis protocols of phosphoramides and extends the application of ionic liquids as green media in the C—H bond functionalization.

Key words: transition metal, ionic liquids, hydrocarbon activation, amidation, regioselectivity, phosphoryl azid

Cite this article

Zihui Ning, Xinhua Peng, Rui Bai, Shanshan Liu, Zhuo Li, Linyu Jiao. Iridium Catalyzed C—H Amidation of Benzamides with Phosphoryl Azides in Ionic Liquids[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4484-4492.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

References 15

[1]	(a) Schwarz, D. M. C.; Williams, S. K.; Dillenburg, M.; Wagner, C. R.; Gestwicki, J. E. ACS Med. Chem. Lett. 2020, 11, 1704. doi: 10.1021/acsmedchemlett.0c00170 pmid: 32944137
	(b) Serpi, M.; Bibbo, R.; Rat, S.; Roberts, H.; Hughes, C.; Caterson, B.; Alcaraz, M. J.; Gibert, A. T.; Verson, C. R. A.; McGuigan, C. J. Med. Chem. 2012, 55, 4629. doi: 10.1021/jm300074y pmid: 32944137
	(c) Roush, R. F.; Nolan, E. M.; Löhr, F.; Walsh, C. T. J. Am. Chem. Soc. 2008, 130, 3603. doi: 10.1021/ja7101949 pmid: 32944137
[2]	(a) Ullmann, F.; Dtsch, B. Chem. Ges. 1903, 36, 2382. doi: 10.1002/cber.v36:2
	(b) Monnier, F.; Taillefer, M. Angew. Chem., Int. Ed. 2009, 48, 6954. doi: 10.1002/anie.v48:38
[3]	(a) Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 7901. doi: 10.1021/ja00096a059
	(b) Paul, F.; Patt, J.; Hartwig, J. F. J. Am. Chem. Soc. 1994, 116, 5969. doi: 10.1021/ja00092a058
	(c) Dorel, R.; Grugel, C. P.; Haydl, A. M. Angew. Chem., Int. Ed. 2019, 58, 17118. doi: 10.1002/anie.v58.48
[4]	(a) Chen, J.-Q.; Li, J.-L.; Dong, Z.-B. Adv. Synth. Catal. 2020, 362, 3311. doi: 10.1002/adsc.v362.16
	(b) West, M. J.; Fyfe, J. W. B.; Vantourout, J. C.; Watson, A. J. B. Chem. Rev. 2019, 119, 12491. doi: 10.1021/acs.chemrev.9b00491
[5]	(a) Park, Y.; Kim, Y.; Chang, S. Chem. Rev. 2017, 117, 9247. doi: 10.1021/acs.chemrev.6b00644
	(b) Wang, X.; Gao, J.; Xu, X.; Fang, P.; Mei, T. Chin. J. Org. Chem. 2021, 41, 384. (in Chinese) doi: 10.6023/cjoc202005021
	(王向阳, 高君青, 徐学涛, 方萍, 梅天胜, 有机化学, 2021, 41, 384.) doi: 10.6023/cjoc202005021
	(c) Ouyang, B.; Zheng, Y.; Xia, K.; Xu, X.; Wang, Y. Chin. J. Org. Chem. 2020, 40, 1188. (in Chinese) doi: 10.6023/cjoc201910002
	(欧阳班来, 郑燕霞, 夏克坚, 徐小玲, 王艺, 有机化学, 2020, 40, 1188.) doi: 10.6023/cjoc201910002
	(d) Wu, M.; Huang, X.; Zhang, H.; Li, P. Chin. J. Org. Chem. 2019, 39, 3114. (in Chinese) doi: 10.6023/cjoc201903029
	(吴梅, 黄新平, 张海兵, 李鹏飞, 有机化学, 2019, 39, 3114.) doi: 10.6023/cjoc201903029
	(e) Sun, Y.; Ding, Q.; Yu, Y.; He, Y.; Huang, F. Chin. J. Org. Chem. 2019, 39, 3363. (in Chinese) doi: 10.6023/cjoc201906026
	(孙义明, 丁奇峰, 于杨, 何益得, 黄菲, 有机化学, 2019, 39, 3363.) doi: 10.6023/cjoc201906026
	(f) Luo, F. Chin. J. Org. Chem. 2019, 39, 3084. (in Chinese) doi: 10.6023/cjoc201905027
	(罗飞华, 有机化学, 2019, 39, 3084.) doi: 10.6023/cjoc201905027
[6]	(a) Nguyen, K. X.; Pham, P. H.; Nguyen, T. T.; Yang, C.-H.; Pham, H. T. B.; Nguyen, T. T.; Wang, H.; Phan, N. T. S. Org. Lett. 2020, 22, 9751. doi: 10.1021/acs.orglett.0c03846
	(b) Zhou, C.; Zhao, J.; Guo, W.; Jiang, J.; Wang, J. Org. Lett. 2019, 21, 9315. doi: 10.1021/acs.orglett.9b03357
[7]	(a) Ng, K.-H.; Zhou, Z.; Yu, W.-Y. Chem. Commun. 2013, 49, 7031. doi: 10.1039/c3cc42937g
	(b) Zhou, B.; Du, J.; Yang, Y.; Li, Y. Org. Lett. 2013, 15, 2934. doi: 10.1021/ol400921r
	(c) Grohmann, C.; Wang, H.; Glorius, F. Org. Lett. 2012, 14, 656. doi: 10.1021/ol203353a
[8]	(a) Mei, R.; Loup, J.; Ackermann, L. ACS Catal. 2016, 6, 793. doi: 10.1021/acscatal.5b02661 pmid: 31478381
	(b) Liang, Y.; Liang, Y.-F.; Tang, C.; Yuan, Y.; Jiao, N. Chem. Eur. J. 2015, 21, 16395. doi: 10.1002/chem.v21.46 pmid: 31478381
	(c) Park, J.; Chang, S. Angew. Chem., Int. Ed. 2015, 54, 14103. doi: 10.1002/anie.201505820 pmid: 31478381
	(d) Ding, J.; Jiang, W.; Bai, H.-Y.; Ding, T.-M.; Gao, D. F.; Bao, X. G.; Zhang, S.-Y. Chem. Commun. 2018, 54, 8889. doi: 10.1039/C8CC04904A pmid: 31478381
	(e) Huang, J.; Ding, J.; Ding, T.-M.; Zhang, S. Y.; Wang, Y. Q.; Sha, F.; Zhang, S.-Y.; Wu, X.-Y.; Li, Q. Org. Lett. 2019, 21, 7342. doi: 10.1021/acs.orglett.9b02632 pmid: 31478381
[9]	(a) Patel, P.; Chang, S. Org. Lett. 2014, 16, 3328. doi: 10.1021/ol501338h
	(b) Patel, P; Chang, S. ACS Catal. 2015, 5, 853. doi: 10.1021/cs501860b
[10]	(a) Lee, J.; Jin, S.; Kim, D.; Hong, S. H.; Chang, S. J. Am. Chem. Soc. 2021, 143, 5191. doi: 10.1021/jacs.1c01524
	(b) Dong, X.; Ma, P.; Zhang, T.; Jalani, H. B.; Li, G.; Lu, H. J. Org. Chem. 2020, 85, 13096. doi: 10.1021/acs.joc.0c01789
	(c) Kim, H.; Park, J.; Kim, J. G.; Chang, S. Org. Lett. 2014, 16, 5466. doi: 10.1021/ol502722j
	(d) Kim, J. Y.; Park, S. H.; Ryu, J.; Cho, S. H.; Kim, S. H.; Chang, S. J. Am. Chem. Soc. 2012, 134, 9110. doi: 10.1021/ja303527m
[11]	(a) Xiao, W.; Zhou, C.-Y.; Che, C.-M. Chem. Commun. 2012, 48, 5871. doi: 10.1039/c2cc31686b
	(b) Pan, C.; Jin, N.; Zhang, H.; Han, J.; Zhu, C. J. Org. Chem. 2014, 79, 9427. doi: 10.1021/jo5018052
	(c) Pan, C. D.; Wang, Y.; Wu, C.; Yu, J.-T. Org. Biomol. Chem. 2018, 16, 3711. doi: 10.1039/C8OB00776D
[12]	(a) Muntzeck, M.; Pippert, F.; Wilhelm, R. Tetrahedron 2020, 76, 131314. doi: 10.1016/j.tet.2020.131314
	(b) Kong, X.; Xu, B. Asian J. Org. Chem. 2019, 8, 1862. doi: 10.1002/ajoc.v8.10
	(c) Li, J.; Zhou, L.; Wang, Y.; Ma, Q.; Lei, Y.; Lai, R.; Luo, Y.; Hai, L.; Wu, Y. Eur. J. Org. Chem. 2019, 2019, 7448. doi: 10.1002/ejoc.201901279
[13]	Ma, Q.; Yu, X.; Lai, R.; Lv, S.; Dai, W.; Zhang, C.; Wang, X.; Wang, Q.; Wu, Y. ChemSusChem 2018, 11, 3672. doi: 10.1002/cssc.v11.20
[14]	Jiao, L.-Y.; Ning, Z.-H.; Hong, Q.; Peng, X.-H.; Yin, X.-M.; Liu, S.; Chen, H.; Li, Z.; Sun, M.; Ma, X.-X. RSC Adv. 2020, 10, 29712. doi: 10.1039/D0RA05527A
[15]	(a) Jiao, L.-Y.; Zhang, Z.; Yin, X.-M.; Li, Z.; Ma, X.-X. J. Catal. 2019, 379, 39. doi: 10.1016/j.jcat.2019.09.014
	(b) Jiao, L.-Y.; Zhang, Z.; Hong, Q.; Ning, Z.-H.; Liu, S.; Sun, M.; Hao, Q.; Xu, L.; Li, Z.; Ma, X.-X. Mol. Catal. 2020, 494, 111120.

Entry	Catalyst	Silver salt	Additive (50 mol%)	Solvent	T/℃	Yield^b/%
1	[IrCp*Cl₂]₂	AgNTf₂	NaOAc	[BMIM]BF₄	r.t.	ND^c
2	[IrCp*Cl₂]₂	AgNTf₂	NaOAc	[BMIM]BF₄	40	Trace
3	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]BF₄	80	38
4	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]BF₄	100	ND^c
5	[IrCp*Cl₂]₂	AgSbF₆	—	[BMIM]BF₄	80	25
6	[IrCp*Cl₂]₂	AgBF₄	—	[BMIM]BF₄	80	Trace
7	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]PF₆	80	ND^c
8	[IrCp*Cl₂]₂	AgNTf₂	Li₂CO₃	[BMIM]BF₄	80	ND^c
9	[IrCp*Cl₂]₂	AgNTf₂	AgOAc	[BMIM]BF₄	80	82
10	[IrCp*Cl₂]₂	AgNTf₂	Ag₂O	[BMIM]BF₄	80	15
11	[IrCp*Cl₂]₂	AgNTf₂	Ag₂CO₃	[BMIM]BF₄	80	Trace
12	[IrCp*Cl₂]₂	AgNTf₂	TFA	[BMIM]BF₄	80	ND^c
13	[IrCp*Cl₂]₂	AgNTf₂	AgOAc	[BMIM]PF₆	80	Trace
14	[RhCp*Cl₂]₂	AgSbF₆	—	[BMIM]PF₆	80	ND^c
15	[RhCp*Cl₂]₂	AgSbF₆	NaOAc	[BMIM]PF₆	80	ND^c
16	[RhCp*Cl₂]₂	—	Li₂CO₃	[BMIM]BF₄	80	ND^c

Entry	Catalyst	Silver salt	Additive (50 mol%)	Solvent	T/℃	Yield^b/%
1	[IrCp*Cl₂]₂	AgNTf₂	NaOAc	[BMIM]BF₄	r.t.	ND^c
2	[IrCp*Cl₂]₂	AgNTf₂	NaOAc	[BMIM]BF₄	40	Trace
3	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]BF₄	80	38
4	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]BF₄	100	ND^c
5	[IrCp*Cl₂]₂	AgSbF₆	—	[BMIM]BF₄	80	25
6	[IrCp*Cl₂]₂	AgBF₄	—	[BMIM]BF₄	80	Trace
7	[IrCp*Cl₂]₂	AgNTf₂	—	[BMIM]PF₆	80	ND^c
8	[IrCp*Cl₂]₂	AgNTf₂	Li₂CO₃	[BMIM]BF₄	80	ND^c
9	[IrCp*Cl₂]₂	AgNTf₂	AgOAc	[BMIM]BF₄	80	82
10	[IrCp*Cl₂]₂	AgNTf₂	Ag₂O	[BMIM]BF₄	80	15
11	[IrCp*Cl₂]₂	AgNTf₂	Ag₂CO₃	[BMIM]BF₄	80	Trace
12	[IrCp*Cl₂]₂	AgNTf₂	TFA	[BMIM]BF₄	80	ND^c
13	[IrCp*Cl₂]₂	AgNTf₂	AgOAc	[BMIM]PF₆	80	Trace
14	[RhCp*Cl₂]₂	AgSbF₆	—	[BMIM]PF₆	80	ND^c
15	[RhCp*Cl₂]₂	AgSbF₆	NaOAc	[BMIM]PF₆	80	ND^c
16	[RhCp*Cl₂]₂	—	Li₂CO₃	[BMIM]BF₄	80	ND^c

Entry	R¹	R²	Product	t/h	Yield^b/%
1	H	Me	5aa	24	66
2	H	n-Pr	5ba	24	56
3	H	i-Pr	5ca	24	50
4	H	Cy	5da	24	48
5	i-Pr	i-Pr	5ea	30	ND^c

Entry	R¹	R²	Product	t/h	Yield^b/%
1	H	Me	5aa	24	66
2	H	n-Pr	5ba	24	56
3	H	i-Pr	5ca	24	50
4	H	Cy	5da	24	48
5	i-Pr	i-Pr	5ea	30	ND^c

Entry	R (1)	Product	t/h	Yield^b/%
1	H (1a)	3aa	24	82
2	3-Me (1b)	3ba	24	56
3	4-Me (1c)	3ca	24	55
4	4-OMe (1d)	3da	36	58
5	4-F (1e)	3ea	24	67
6	4-Cl (1f)	3fa	30	65
7	4-Br (1g)	3ga	30	56
8	4-NO₂ (1h)	3ha	30	73

铱催化的苯甲酰胺和磷酰叠氮在离子液体中的C—H键胺化反应