N-Heterocyclic Carbene (NHC)-Catalyzed [4+3] Cycloaddition to Synthesize 4-Aminobenzoheptenolactons

doi:10.6023/cjoc202301011

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (3): 1084-1090.DOI: 10.6023/cjoc202301011 Previous Articles Next Articles

Special Issue: 中国女科学家专辑

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氮杂环卡宾(NHC)催化[4+3]环加成反应构建4-氨基苯并环庚烯内酯

戴春波, 夏思奇, 陈晓玉, 杨丽敏^*()

杭州师范大学材料与化学化工学院有机硅化学及材料技术教育部重点实验室杭州 311121

收稿日期:2023-01-10 修回日期:2023-02-20 发布日期:2023-02-27
通讯作者: 杨丽敏
作者简介:
† 共同第一作者.
基金资助:
国家自然科学基金(22271071); 浙江省自然科学基金(LY20B020010)

N-Heterocyclic Carbene (NHC)-Catalyzed [4+3] Cycloaddition to Synthesize 4-Aminobenzoheptenolactons

Chunbo Dai, Siqi Xia, Xiaoyu Chen, Limin Yang()

Key Laboratory of Organosilicon Chemistry and Material Technology, Ministry of Education, College of Materials, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 311121

Received:2023-01-10 Revised:2023-02-20 Published:2023-02-27
Contact: Limin Yang
About author:
† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22271071); Natural Science Foundation of Zhejiang Province(LY20B020010)

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Abstract

A highly efficient N-heterocyclic carbene (NHC) catalyzed formal [3+4] cycloaddition reaction of γ-chloroenal with iminoquinones has been developed, producing 4-aminobenzoheptenolactone derivatives in good yields. In order to explore the role of nitroheterocyclic carbene in the site selectivity of the reaction, a theoretical study was carried out using density functional theory. The study showed that the deformation force was the main reason for the difference in site selection.

Key words: N-heterocyclic carbene (NHC), organocatalysis, [4+3] cycloaddition, site selectivity, 4-aminobenzoheptenolactone

Cite this article

Chunbo Dai, Siqi Xia, Xiaoyu Chen, Limin Yang. N-Heterocyclic Carbene (NHC)-Catalyzed [4+3] Cycloaddition to Synthesize 4-Aminobenzoheptenolactons[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1084-1090.

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Fig. & Tab. 7

References 14

[1]	(a) Yu, Y.; Pushkin, C.; Song, J.; Zhu, L.; Li, C.; Huang, X. Nat. Commun. 2020, 11, 461. doi: 10.1038/s41467-019-14101-5
	(b) Fan, X.-D.; Wang, G.-W.; Wang, H.; Mao, J.-X.; Lan, X.-Z.; Miao, Z.-H.; Chen, M. Chin. Acta Pharm Sin. 2016, 51, 770. (in Chinese)
	(范旭东, 王国伟, 王红, 毛景欣, 兰小中, 廖志华, 陈敏, 药学学报, 2016, 51, 770.)
[2]	(a) Schleyer, P. V. R.; Williams, J. E.; Blanchard, K. R. J. Am. Chem. Soc. 1970, 92, 2377. doi: 10.1021/ja00711a030
	(b) Xu, H.; Hu, J.; Wang, L.; Liao, S.; Tang, Y. J. Am. Chem. Soc. 2015, 137, 8006. doi: 10.1021/jacs.5b04429
	(c) Hu, Y.; Li, L.; Han, J.; Min, L.; Li, C. Chem. Rev. 2020, 120, 5910. doi: 10.1021/acs.chemrev.0c00045
[3]	(a) Rezai, T.; Yu, B.; Millhauser, G. L.; Jacobson, M. P.; Lokey, R. J. Am. Chem. Soc. 2006, 128, 2510. pmid: 16492015
	(b) Hung, K.; Hu, X.; Maimone, T. J. Nat. Prod. Rep. 2018, 35, 174. doi: 10.1039/C7NP00065K pmid: 16492015
	(c) Wang, L.-N.; Yu, Z.-X. Chin. J. Org. Chem. 2020, 40, 3536. (in Chinese) doi: 10.6023/cjoc202010025 pmid: 16492015
	(王路宁, 余志祥, 有机化学, 2020, 40, 3536.) doi: 10.6023/cjoc202010025 pmid: 16492015
	(d) Reyes, R. L.; Iwai, T.; Sawamura, M. Chem. Rev. 2021, 121, 8926. doi: 10.1021/acs.chemrev.0c00793 pmid: 16492015
[4]	Illuminati, G.; Mandolini, L. Acc. Chem. Res. 1981, 14, 95. doi: 10.1021/ar00064a001
[5]	(a) Butenschon, H. Angew. Chem., Int. Ed. 2008, 47, 5287 doi: 10.1002/anie.v47:29 pmid: 33576620
	(b) Yet, L. Chem. Rev. 2000, 100, 2963. pmid: 33576620
	(c) Doerksen, R.S.; Hodik, T.; Hu, G.; Huynh, N. O.; Shuler, Q. W. G.; Krische, M. J. Chem. Rev. 2021, 121, 4045. doi: 10.1021/acs.chemrev.0c01133 pmid: 33576620
[6]	(a) Meng, D.; Xie, Y.; Peng, Q.; Wang, J. Org. Lett. 2020, 22, 7635. doi: 10.1021/acs.orglett.0c02832 pmid: 32964708
	(b) Wang, J.; Zhao, C.; Wang, J. ACS Catal. 2021, 11, 12520. doi: 10.1021/acscatal.1c03459 pmid: 32964708
	(c) Gao, J.; Feng, J.; Du, D. Org. Chem. Front. 2021, 8, 6138. doi: 10.1039/D1QO01127H pmid: 32964708
	(d) Pavithra, T.; Devi, E.; Maheswari, C. Asian J. Org. Chem. 2021, 10, 1861. doi: 10.1002/ajoc.v10.8 pmid: 32964708
[7]	Burstein, C.; Glorius, F. Angew. Chem., Int. Ed. 2004, 43, 6205. doi: 10.1002/(ISSN)1521-3773
[8]	Sohn, S.; Rosen, E.; Bode, J. J. Am. Chem. Soc. 2004, 126, 14370. doi: 10.1021/ja044714b
[9]	(a) Ghosh, A.; Barik, S.; Biju. A. Org. Lett. 2019, 21, 8598. doi: 10.1021/acs.orglett.9b03188 pmid: 32312044
	(b) Dzieszkowski, K.; Baranska. I.; Rafinski. Z. J. Org. Chem. 2020, 85, 6645. doi: 10.1021/acs.joc.0c00657 pmid: 32312044
	(c) Duan, X.; Tian, Z.; Liu, B.; He, T.; Zhao, L.; Dong, M.; Zhang, P.; Qi, J. Org. Lett. 2021, 23, 3777. doi: 10.1021/acs.orglett.1c01203 pmid: 32312044
[10]	(a) Xie, D.; Yang, L.; Lin, Y.; Zhang, Z.; Chen, D.; Zeng, X.; Zhong, G. Org. Lett. 2015, 17, 2318. doi: 10.1021/acs.orglett.5b00726
	(b) Lin, Y.; Yang, L.; Deng, Y.; Zhong, G. Chem. Commun. 2015, 51, 8330. doi: 10.1039/C5CC02096D
[11]	(a) Zhang, Y.; Lv, H.; Zhou, D.; Ye, S. Chem.-Eur. J. 2008, 14, 8473. doi: 10.1002/chem.v14:28
	(b) Lv, H.; You, L.; Ye, S. Adv. Synth. Catal. 2009, 351, 2822. doi: 10.1002/adsc.v351:17
	(c) Huang, X.; He, L.; Shao, P.; Ye, S. Angew. Chem., Int. Ed. 2009, 48, 192.
	(d) Mo, J.; Chen, X.; Chi, Y. J. Am. Chem. Soc. 2012, 134, 8810. doi: 10.1021/ja303618z
	(e) Yao, C.; Xiao, Z.; Liu, R.; Li, T.; Jiao, W.; Yu, C. Chem.-Eur. J. 2013, 19, 456. doi: 10.1002/chem.201202655
[12]	Yan, J.; Song, Z.; Zhao, C.; Shi, K.; Yang, L.; Zhong, G. Org. Lett. 2020, 22, 9, 3329.
[13]	Lv, H.; Jia, W.; Sun, L.; Ye, S. Angew. Chem., Int. Ed. 2013, 52, 8607. doi: 10.1002/anie.201303903
[14]	Izquierdo, J.; Orue, A.; Scheidt, K. A. J. Am. Chem. Soc. 2013, 135, 10634. doi: 10.1021/ja405833m pmid: 23829462

Entry	Solvent	Cat.	Base	T/℃	Yield^b/%
1	THF	Cat. A	TEA	r.t	30
2	THF	Cat. B	TEA	r.t	35
3	THF	Cat. C	TEA	r.t	<10
4	THF	Cat. D	TEA	r.t	Trace
5	THF	Cat. E	TEA	r.t	Trace
6	THF	Cat. F	TEA	r.t	Trace
7	THF	Cat. G	TEA	r.t	Trace
8	THF	Cat. B	DIPEA	r.t	Trace
9	THF	Cat. B	DABCO	r.t	Trace
10	THF	Cat. B	DMAP	r.t	Trace
11	THF	Cat. B	DBU	r.t	Trace
12	THF	Cat. B	Na₂CO₃	r.t	20
13	THF	Cat. B	NaOAc	r.t	40
14	THF	Cat. B	Cs₂CO₃	r.t	22
15	THF	Cat. B	NaHCO₃	r.t	<10
16	THF	Cat. B	K₂CO₃	r.t	<10
17	DCM	Cat. B	NaOAc	r.t	65
18	DCE	Cat. B	NaOAc	r.t	52
19	CHCl₃	Cat. B	NaOAc	r.t	56
20	Et₂O	Cat. B	NaOAc	r.t	64
21	Toluene	Cat. B	NaOAc	r.t	74
22	1,4-Dioxane	Cat. B	NaOAc	r.t	Trace
23	EA	Cat. B	NaOAc	r.t	50
24	MTBE	Cat. B	NaOAc	r.t	<10
25	MeCN	Cat. B	NaOAc	r.t	<10
26	Toluene	Cat. B	NaOAc	0	30
27	Toluene	Cat. B	NaOAc	30	70
28^c	Toluene	Cat. B	NaOAc	r.t	51
29^d	Toluene	Cat. B	NaOAc	r.t	70

Entry	Solvent	Cat.	Base	T/℃	Yield^b/%
1	THF	Cat. A	TEA	r.t	30
2	THF	Cat. B	TEA	r.t	35
3	THF	Cat. C	TEA	r.t	<10
4	THF	Cat. D	TEA	r.t	Trace
5	THF	Cat. E	TEA	r.t	Trace
6	THF	Cat. F	TEA	r.t	Trace
7	THF	Cat. G	TEA	r.t	Trace
8	THF	Cat. B	DIPEA	r.t	Trace
9	THF	Cat. B	DABCO	r.t	Trace
10	THF	Cat. B	DMAP	r.t	Trace
11	THF	Cat. B	DBU	r.t	Trace
12	THF	Cat. B	Na₂CO₃	r.t	20
13	THF	Cat. B	NaOAc	r.t	40
14	THF	Cat. B	Cs₂CO₃	r.t	22
15	THF	Cat. B	NaHCO₃	r.t	<10
16	THF	Cat. B	K₂CO₃	r.t	<10
17	DCM	Cat. B	NaOAc	r.t	65
18	DCE	Cat. B	NaOAc	r.t	52
19	CHCl₃	Cat. B	NaOAc	r.t	56
20	Et₂O	Cat. B	NaOAc	r.t	64
21	Toluene	Cat. B	NaOAc	r.t	74
22	1,4-Dioxane	Cat. B	NaOAc	r.t	Trace
23	EA	Cat. B	NaOAc	r.t	50
24	MTBE	Cat. B	NaOAc	r.t	<10
25	MeCN	Cat. B	NaOAc	r.t	<10
26	Toluene	Cat. B	NaOAc	0	30
27	Toluene	Cat. B	NaOAc	30	70
28^c	Toluene	Cat. B	NaOAc	r.t	51
29^d	Toluene	Cat. B	NaOAc	r.t	70

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氮杂环卡宾(NHC)催化[4+3]环加成反应构建4-氨基苯并环庚烯内酯

N-Heterocyclic Carbene (NHC)-Catalyzed [4+3] Cycloaddition to Synthesize 4-Aminobenzoheptenolactons

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