碱催化α-氰基-β-甲基烯基(杂)芳基酮苯增环反应合成多取代苯

doi:10.6023/cjoc202104056

有机化学 ›› 2021, Vol. 41 ›› Issue (9): 3625-3632.DOI: 10.6023/cjoc202104056 上一篇下一篇

研究论文

碱催化α-氰基-β-甲基烯基(杂)芳基酮苯增环反应合成多取代苯

安逸, 张放, 蔡志华, 杜广芬^*()

石河子大学化工学院新疆兵团化工绿色过程重点实验室新疆石河子 832000

收稿日期:2021-04-27 修回日期:2021-06-07 发布日期:2021-06-29
通讯作者: 杜广芬
基金资助:
国家自然科学基金(21662029); 兵团优秀青年教师(2017CB001); 兵团优秀青年教师(CZ027203); 石河子大学国际合作(GJHZ201801)

Direct Assembly of Polysubstituted Benzenes via Base-Catalyzed Benzannulation Reaction of α-Cyano-β-methylalkenyl-(hetero)aryl Ketones

Yi An, Fang Zhang, Zhihua Cai, Guangfen Du()

Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832000

Received:2021-04-27 Revised:2021-06-07 Published:2021-06-29
Contact: Guangfen Du
Supported by:
National Natural Science Foundation of China(21662029); Excellent Young Teachers Plan of Bingtuan(2017CB001); Excellent Young Teachers Plan of Bingtuan(CZ027203); International Cooperation Project of Shihezi University(GJHZ201801)

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摘要/Abstract

发展了一种非金属催化下高效构筑多取代苯的新方法. 以10 mol%的Cs₂CO₃为催化剂, 一系列α-氰基-β-甲基烯基(杂)芳基酮可在极其温和的反应条件下与丁炔二酸酯发生[4+2]环加成/脱水芳构化苯增环反应, 以62%~94%的收率生成1,2-二酯基-3-(杂)芳基-4-氰基苯衍生物.

关键词: α-氰基-β-甲基烯基(杂)芳基酮, 丁炔二酸酯, [4+2]环加成反应, 1,2-二酯基-3-(杂)芳基-4-氰基苯衍生物

A mild and transition-metal free method for rapid construction of benzene frameworks has been developed. Under the catalysis of 10 mol% Cs₂CO₃, a variety of α-cyano-β-methylalkenyl(hetero)aryl ketones undergo [4+2] annulation with different dialkyl butynedioates efficiently to produce 1,2-diesteryl-3-(hetero)aryl-4-cyanobenzene derivatives in 62%~94% yields.

Key words: α-cyano-β-methylalkenyl(hetero)aryl ketones, dialkyl butynedioates, [4+2] annulation, 1,2-diesteryl-3-(hetero)- aryl-4-cyanobenzene derivatives

引用此文

安逸, 张放, 蔡志华, 杜广芬. 碱催化α-氰基-β-甲基烯基(杂)芳基酮苯增环反应合成多取代苯[J]. 有机化学, 2021, 41(9): 3625-3632.

Yi An, Fang Zhang, Zhihua Cai, Guangfen Du. Direct Assembly of Polysubstituted Benzenes via Base-Catalyzed Benzannulation Reaction of α-Cyano-β-methylalkenyl-(hetero)aryl Ketones[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3625-3632.

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[1]	(a) Lvan Otterlo, W. A. L.; de Koning, C. B. Chem. Rev. 2009, 109, 3743. doi: 10.1021/cr900178p pmid: 19618929
	(b) Fuhr, L.; Rousseau, M.; Plauth, A.; Schroeder, F. C.; Sauer, S. J. Nat. Prod. 2015, 78, 1160. doi: 10.1021/np500747y pmid: 19618929
	(c) Boland, S.; Bourin, A.; Alen, J.; Geraets, J.; Schroeders, P.; Castermans, K.; Kindt, N.; Boumans, N.; Panitti, L.; Fransen, S.; Vanormel ingen, J.; Stassen, J. M.; Leysen, D.; Defert, O. J. Med. Bioorg. Chem. Lett. 2015, 58, 4309. pmid: 19618929
	(d) Shirota, Y. J. Mater. Chem. 2005, 15, 75. doi: 10.1039/B413819H pmid: 19618929
[2]	(a) Kirkham, J. D.; Butlin, R. J.; Harrity, J. P. A. Angew. Chem., Int. Ed. 2012, 51, 6402. doi: 10.1002/anie.201200917 pmid: 18321122
	(b) Fillion, E.; Dumas, A. M. J. Org. Chem. 2008, 73, 2920. doi: 10.1021/jo702591p pmid: 18321122
[3]	(a) Ritleng, V.; Sirlin, C.; Pfeffer, M. Chem. Rev. 2002, 102, 1731. doi: 10.1021/cr0104330 pmid: 23789920
	(b) Ciana, C. L.; Phipps, R. J.; Brandt, J. R.; Meyer, F. M.; Gaunt, M. J. Angew. Chem., Int. Ed. 2011, 50, 458. doi: 10.1002/anie.201004703 pmid: 23789920
	(c) Gustafson, J. L.; Lim, D.; Barrett, K. T.; Miller, S. J. Angew. Chem., Int. Ed. 2011, 50, 5125. doi: 10.1002/anie.v50.22 pmid: 23789920
	(d) Zhao, F.; Zhang, Y.-F.; Wen, J.; Yu, D.-G.; Wei, J.-B.; Xi, Z.; Shi, Z.-J. Org. Lett. 2013, 15, 3230. doi: 10.1021/ol4011757 pmid: 23789920
[4]	(a) Roglans, A.; Pla-Quintana, A.; SolÃ, M. Chem. Rev. 2021, 121, 1894. doi: 10.1021/acs.chemrev.0c00062 pmid: 30125114
	(b) Chien, C.-W.; Teng Gary, Y.-H.; Honda, T.; Ojima, I. J. Org. Chem. 2018, 83, 11623. doi: 10.1021/acs.joc.8b01608 pmid: 30125114
	(c) Okamoto, S.; Yamada, T.; Tanabe, Y. K.; Sakai, M. Organometallics 2018, 37, 4431. doi: 10.1021/acs.organomet.8b00678 pmid: 30125114
	(d) More, A. A.; Ramana, C. V. J. Org. Chem. 2016, 81, 3400. doi: 10.1021/acs.joc.6b00020 pmid: 30125114
	(e) García-Lacuna, J.; Domínguez, G.; Blanco-Urgoiti, J.; Perez-Castells, J. Org. Lett. 2018, 20, 5219. doi: 10.1021/acs.orglett.8b02168 pmid: 30125114
	(f) Méndez-Gálvez, C.; Böhme, M.; Leino, R.; SavelaEur, R. J. Org. Chem. 2020, 11, 1708. pmid: 30125114
[5]	(a) Hein, S. J.; Lehnherr, D.; Arslan, H.; Uribe, F. J.; Dichtel, W. R. Acc. Chem. Res. 2017, 50, 2776. doi: 10.1021/acs.accounts.7b00385
	(b) Poudel, T. N.; Tamargo, R. J. I.; Cai, H.; Lee, Y. R. Asian J. Org. Chem. 2018, 7, 985. doi: 10.1002/ajoc.v7.6
	(c) Takikawa, H.; Nishii, A.; Takiguchi, H.; Yagishita, H.; Tanaka, M.; Hirano, K.; Uchiyama, M.; Ohmori, K.; Suzuki, K. Angew. Chem., Int. Ed. 2020, 59, 12440. doi: 10.1002/anie.v59.30
	(d) Song, C. L.; Dong, X.; Wang, Z. J.; Liu, K.; Chiang, C. W.; Lei, A. W. Angew. Chem., Int. Ed. 2019, 58, 12206. doi: 10.1002/anie.v58.35
[6]	(a) Jia, Q. F.; Lin, Y. Q.; Li, Y. H. Chin. J. Org. Chem. 2020, 40, 1502. (in Chinese). doi: 10.6023/cjoc202001011
	( 贾乾发, 李娅琼, 林银河, 有机化学, 2020, 40, 1502.)
	(b) Wang, D.; Lin, J. H.; Zhu, Y. N.; Huang, Y. Adv. Synth. Catal. 2021, 363, 1873. doi: 10.1002/adsc.v363.7
	(c) Wu, J. C.; Mou, C.-L.; Chi, Y. G. Chin. J. Chem. 2018, 36, 333. doi: 10.1002/cjoc.v36.4
	(d) Chang, M. J.; Huang, Y. Chem. Asian J. 2019, 14, 2588. doi: 10.1002/asia.v14.15
	(e) Shu, W. M.; Zheng, K. L.; Ma, J. R.; Wu, A. X. Org. Lett. 2015, 17, 5216. doi: 10.1021/acs.orglett.5b02548
	(f) Jia, F. C.; Xu, C.; Zhou, Z. W.; Cai, Q.; Wu, Y. D.; Wu, A. X. Org. Lett. 2016, 18, 5232. doi: 10.1021/acs.orglett.6b02515
	(g) Zhou, Q.-F.; Xin, B.-T.; Lu, T.; Xue, S. Chin. J. Org. Chem. 2009, 29, 1462. (in Chinese).
	( 周庆发, 辛波涛, 陆涛, 薛松, 有机化学, 2009, 29, 1462.)
[7]	(a) Zhang, C. L.; Ye, S. Org. Lett. 2016, 18, 6408. doi: 10.1021/acs.orglett.6b03306
	(b) Jia, Q.; Wang, J. Org. Lett. 2016, 18, 2212. doi: 10.1021/acs.orglett.6b00844
[8]	Zhang, C. L.; Gao, Z. H.; Liang, Z. Q.; Ye, S. Adv. Synth. Catal. 2016, 358, 2862. doi: 10.1002/adsc.v358.18
[9]	Zhang, C. L.; Zhang, Z.-F.; Xia, Z. H.; Han, Y. F.; Ye, S. J. Org. Chem. 2018, 83, 12507. doi: 10.1021/acs.joc.8b01740
[10]	Zhu, C. Z.; Wei, Y.; Shi, M. Adv. Synth. Catal. 2018, 360, 808. doi: 10.1002/adsc.v360.4
[11]	(a) Wang, W. H.; Wan, H. W.; Du, G. F.; Dai, B.; He, L. Org. Lett. 2019, 21, 3496. doi: 10.1021/acs.orglett.9b00659
	(b) Pian, J. X.; He, L.; Du, G. F.; Guo, H.; Dai, B. J. Org. Chem. 2014, 79, 5820. doi: 10.1021/jo5003399
	(c) Xie, P.; Yang, S. S.; Guo, Y. Y.; Cai; Z. H.; Dai; B.; He, L. J. Org. Chem. 2020, 85, 8872. doi: 10.1021/acs.joc.0c00745
	(d) Li, Z. J.; Wang, W. H.; Jian, H.; Li, W.J.; Dai; B.; He, L. Chin. Chem. Lett. 2019, 30, 386. doi: 10.1016/j.cclet.2018.04.003
	(e) Feng, Z. N.; Luo, J. Y.; Zhang, Y.; Du, G.-F.; He, L. Org. Biomol. Chem. 2019, 17, 4700. doi: 10.1039/C9OB00210C
[12]	Wang, Q.; An, Y.; Du, G. F.; Cai, Z. H.; Dai, B.; He, L. J. Org. Chem. 2020, 85, 14210. doi: 10.1021/acs.joc.0c01975
[13]	For more X-ray crystal structure information of 3a CCDC:2077708) see Supporting Information. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Entry	Base	Time/h	Solvent	Yield ^b/%
1	Cs₂CO₃ (20 mol%)	3	CH₃CN	84
2	Na₂CO₃ (20 mol%)	5	CH₃CN	73
3	K₂CO₃ (20 mol%)	5	CH₃CN	80
4	NaOH (20 mol%)	5	CH₃CN	75
5	KOH (20 mol%)	5	CH₃CN	83
6	Et₃N (20 mol%)	4	CH₃CN	72
7	DIPEA (20 mol%)	12	CH₃CN	83
8	DBU (20 mol%)	5	CH₃CN	90
9	AcONa (20 mol%)	36	CH₃CN	85
10	CS₂CO₃ (50 mol%)	3	CH₃CN	77
11	CS₂CO₃ (10 mol%)	3	CH₃CN	94
12	Et₃N (10 mol%)	5	CH₃CN	89
13	DBU (10 mol%)	5	CH₃CN	92
14	Cs₂CO₃ (5 mol%)	5	CH₃CN	75
15	Cs₂CO₃ (10 mol%)	24	Toluene	30
16	Cs₂CO₃ (10 mol%)	5	CH₂Cl₂	70
17	Cs₂CO₃ (10 mol%)	3	ClCH₂CH₂Cl	70
18	Cs₂CO₃ (10 mol%)	4	1,4-Dioxane	78
19^c	Cs₂CO₃ (10 mol%))	3	CH₃CN	93
20	No base	24	CH₃CN	0

Entry	Base	Time/h	Solvent	Yield ^b/%
1	Cs₂CO₃ (20 mol%)	3	CH₃CN	84
2	Na₂CO₃ (20 mol%)	5	CH₃CN	73
3	K₂CO₃ (20 mol%)	5	CH₃CN	80
4	NaOH (20 mol%)	5	CH₃CN	75
5	KOH (20 mol%)	5	CH₃CN	83
6	Et₃N (20 mol%)	4	CH₃CN	72
7	DIPEA (20 mol%)	12	CH₃CN	83
8	DBU (20 mol%)	5	CH₃CN	90
9	AcONa (20 mol%)	36	CH₃CN	85
10	CS₂CO₃ (50 mol%)	3	CH₃CN	77
11	CS₂CO₃ (10 mol%)	3	CH₃CN	94
12	Et₃N (10 mol%)	5	CH₃CN	89
13	DBU (10 mol%)	5	CH₃CN	92
14	Cs₂CO₃ (5 mol%)	5	CH₃CN	75
15	Cs₂CO₃ (10 mol%)	24	Toluene	30
16	Cs₂CO₃ (10 mol%)	5	CH₂Cl₂	70
17	Cs₂CO₃ (10 mol%)	3	ClCH₂CH₂Cl	70
18	Cs₂CO₃ (10 mol%)	4	1,4-Dioxane	78
19^c	Cs₂CO₃ (10 mol%))	3	CH₃CN	93
20	No base	24	CH₃CN	0

Entry	Ketone	Product	3, Yield^b/% of 3
1			3a, 94 (92)^c
2			3b, 75
3			3c, 91
4			3d, 89
5			3e, 90
6			3f, 84
7			3g, 90
8			3h, 75
Entry	Ketone	Product	3, Yield^b/% of 3
9			3i, 89
10			3j, 82
11			3k, 73
12			3l, 81
13			3m, 80
14			3n, 75
15			3o, 72
16			3p, 87
17			3q, 80
Entry	Ketone	Product	3, Yield^b/% of 3
18			3r, 81
19			3s, 92
20			3t, 90
21^d		—	ND
22		—	ND
23		—	ND
24		—	ND

Entry	Ketone	Product	3, Yield^b/% of 3
1			3a, 94 (92)^c
2			3b, 75
3			3c, 91
4			3d, 89
5			3e, 90
6			3f, 84
7			3g, 90
8			3h, 75
Entry	Ketone	Product	3, Yield^b/% of 3
9			3i, 89
10			3j, 82
11			3k, 73
12			3l, 81
13			3m, 80
14			3n, 75
15			3o, 72
16			3p, 87
17			3q, 80
Entry	Ketone	Product	3, Yield^b/% of 3
18			3r, 81
19			3s, 92
20			3t, 90
21^d		—	ND
22		—	ND
23		—	ND
24		—	ND

碱催化α-氰基-β-甲基烯基(杂)芳基酮苯增环反应合成多取代苯

Direct Assembly of Polysubstituted Benzenes via Base-Catalyzed Benzannulation Reaction of α-Cyano-β-methylalkenyl-(hetero)aryl Ketones

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