碘催化烯烃与活性亚甲基化合物的分子间环丙烷化反应

doi:10.6023/cjoc202502038

摘要/Abstract

发展了一种在碱性环境中以I₂/叔丁基过氧化氢(TBHP)为催化体系的环丙烷化合成策略, 通过活性亚甲基化合物氰基酰胺与苯乙烯或1,4-萘醌为底物, 在无需柱层析步骤下, 以良好的产率合成了一系列多样性环丙烷化合物. 该方法在无过渡金属条件下, 仅需催化量碘参与, 具有原料简单易得, 反应条件绿色温和, 后处理操作简单, 高原子经济性等优点, 为简单高效的绿色合成环丙烷衍生物提供了新的途径.

关键词: 环丙烷, 无过渡金属, 碘, 环丙烷化

A novel strategy was developed for the synthesis of cyclopropane using the I₂/tert-butyl hydroperoxide (TBHP) catalytic system in an alkaline environment. The active methylene compounds, such as cyanoamide and styrene or 1,4-naph- thoquinone were utilized as substrates, and thereby a series of diverse cyclopropane compounds were synthesized in good yields with the absence of column chromatography steps. This approach only required catalytic amount of iodine under transition metal-free conditions, which exhibited the merits of simplicity and readily available starting materials, green and mild reaction conditions, simple post-treatment operations as well as high atom economy. This strategy is expected to provide an innovative route for the facile and efficient green synthesis of cyclopropane derivatives.

Key words: cyclopropane, transition-metal-free, iodine, cyclopropanation

引用此文

赵宇含, 马惠敏, 戈书林, 孔令斌. 碘催化烯烃与活性亚甲基化合物的分子间环丙烷化反应[J]. 有机化学, 2025, 45(9): 3469-3477.

Yuhan Zhao, Huimin Ma, Shulin Ge, Lingbin Kong. Iodine-Catalyzed Intermolecular Cyclopropanation of Olefins with Active Methylene Compounds[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3469-3477.

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[9]	(d) Donslund, B. S.; Jessen, N. I.; Jakobsen, J. B.; Monleón, A.; Nielsena, R. P.; Jørgensen, K. A. Chem. Commun. 2016, 52, 12474.
	(e) Luo, J.; Wu, B.; Chen, M.-W.; Jiang, G.-F.; Zhou, Y.-G. Org. Lett. 2014, 16, 2578.
	(f) Liu, M.-S.; Du, H.-W.; Cui, J.-F.; Shu, W. Angew. Chem., Int. Ed. 2022, 61, e202209929.
[10]	(a) Herraiz, A. G.; Suero, M. G. Synthesis 2019, 51, 2821. pmid: 30543264
	(b) Yang, Z.; Stivanin, M. L.; Jurberg, I. D.; Koenigs, R. M. Chem. Soc. Rev. 2020, 49, 6833. pmid: 30543264
	(c) Durka, J.; Turkowska, J.; Gryko, D. ACS Sustainable Chem. Eng. 2021, 9, 8895. pmid: 30543264
	(d) Cai, B.; Xuan, J. Chin. J. Org. Chem. 2021, 41, 4565 (in Chinese). pmid: 30543264
	(蔡宝贵, 宣俊, 有机化学, 2021, 41, 4565.) doi: 10.6023/cjoc202109040 pmid: 30543264
	(e) Tay, N. E. S.; Lehnherr, D.; Rovis, T. Chem. Rev. 2022, 122, 2487. pmid: 30543264
	(f) Ciszewski, Ł.W.; Rybicka-Jasinska, K.; Gryko, D. Org. Biomol. Chem. 2019, 17, 432. doi: 10.1039/c8ob02703j pmid: 30543264
	(g) Empel, C.; Pei, C.; Koenigs, R. M. Chem. Commun. 2022, 58, 2788. pmid: 30543264
[11]	(a) Jie, L.-H.; Guo, B.; Song, J.; Xu, H.-C. J. Am. Chem. Soc. 2022, 144, 2343. pmid: 36607827
	(b) Fischer, D. M.; Lindner, H.; Amberg, W. M.; Carreira, E. M. J. Am. Chem. Soc. 2023, 145, 774. doi: 10.1021/jacs.2c11680 pmid: 36607827
[12]	Chander, M.; Ram, S.; Sharma, P. K. Asian J. Org. Chem. 2023, 12, e202200616.
[13]	Mondal, A.; Samanta, S. Asian J. Org. Chem. 2021, 10, 2503.
[14]	(a) Cavallo, G.; Metrangolo, P.; Milani, R.; Pilati, T.; Priimagi, A.; Resnati, G.; Terraneo, G. Chem. Rev. 2016, 116, 2478. pmid: 27465662
	(b) Bulfield, D.; Huber, S. M. Chem.-Eur. J. 2016, 22, 14434. doi: 10.1002/chem.201601844 pmid: 27465662
	(c) Breugst, M.; von der Heiden, D.; Schmauck, J. Synthesis 2017, 49, 3224. pmid: 27465662
	(d) Mennie, K. M.; Banik, S. M.; Reichert, E. C.; Jacobsen, E. N. J. Am. Chem. Soc. 2018, 140, 4797. pmid: 27465662
	(e) Uyanik, M.; Sasakura, N.; Mizuno, M.; Ishihara, K. ACS Catal. 2017, 7, 872. pmid: 27465662
	(f) Muniz, K.; Barreiro, L.; Romero, R. M.; Martinez, C. J. Am. Chem. Soc. 2017, 139, 4354. pmid: 27465662
	(g) Domingo, L. R.; Seif, A.; Mazarei, E.; Zahedi, E.; Ahmadi, T. S. New J. Chem. 2020, 44, 19002. doi: 10.1039/d0nj04203j pmid: 27465662
	(h) Uyanik, M.; Okamoto, H.; Yasui, T.; Ishihara, K. Science 2010, 328, 1376. pmid: 27465662
[15]	(a) Britto, K. J.; Meenakshia, M.; Srinivasan, K. RSC Adv. 2024, 14, 22076.
	(b) He, Z.-Y.; Ning, Y.; Zhao, Y.-F.; Diao, H.-L.; Zou, P.; Wang, W.-B.; Shu, J.-S.; Xu, H. Synth. Commun. 2022, 52, 2322.
	(c) Krech, A.; Laktsevich-lskryk, M.; Deil, N.; Fokin, M.; Kimm, M.; Ošeka, M. Chem. Commun. 2024, 60, 14026.
	(d) Yavari, I.; Hosseinpour, R.; Skpilika, S. Synlett 2015, 26, 380.
	(e) Poudel, D. P.; Pokhrel, A.; Tak, R. K.; Shankar, M.; Giri, R. Science 2023, 381, 545.
[16]	Wang, Y.; Han, J.; Chen, J.; Cao, W. Chem. Commun. 2016, 52, 6817.
[17]	Xia, L.; Lee, Y. R. Adv. Synth. Catal. 2013, 355, 2361.
[18]	Yoshimura, A.; Koski, S. R.; Kastern, B. J.; Fuchs, J. M.; Jones, T. N.; Yusubova, R. Y.; Nemykin, V. N.; Zhdankin, V. V. Adv. Synth. Catal. 2014, 356, 3336.
[19]	Kamimura, A.; Takeuchi, R.; Ikeda, K.; Moriyama, T.; Sumimoto, M. J. Org. Chem. 2012, 77, 2236. doi: 10.1021/jo202489v pmid: 22283159
[20]	(a) Condit, I. J.; Fanders, S. E. Science 1945, 102, 128. pmid: 17777365
	(b) Datta, P.; Roy, D.; Jain, D.; Kumar, S.; Sil, S.; Bhunia, A.; Dsagupta, J.; Mandal, S. K. ACS Catal. 2024, 14, 3420. pmid: 17777365
[21]	Nam, S. B.; Khatun, N.; Kang, Y. W.; Park, B. Y.; WooS, K. Chem. Commun. 2020, 56, 2873.
[22]	(a) Miller, R. A.; Hoerrner, R. S. Org. Lett. 2003, 5, 285. pmid: 12556173
	(b) Barluenga, J.; Gonzalez-Bobes, F.; Gonzalez, J. M. Angew. Chem., Int. Ed. 2002, 114, 2668. pmid: 12556173
[23]	Tekale, S. U.; Kauthale, S. S.; Dake, S. A.; Sarda, S. R.; Pawar, R. P. Curr. Org. Chem. 2012, 16, 1485.
[1]	(a) Meijere, A. D.; Kozhushkov, S. I. Chem. Rev. 2000, 100, 93. pmid: 29202408
	(b) Bajaj, P.; Gopeekrishnan, S.; Tyagi, V. Fasan, R. Angew. Chem., Int. Ed. 2016, 55, 16110. pmid: 29202408
	(c) Gnad, F.; Reiser, O. Chem. Rev. 2003, 103, 1603. pmid: 29202408
	(d) Ghosh, A. K.; Reddy, G. C.; Kovela, S.; Relitti, N.; Urabe, V. K.; Prichard, B. E.; Jurica, M. S. Org. Lett. 2018, 20, 7293. doi: 10.1021/acs.orglett.8b03228 pmid: 29202408
	(e) Medvedeva, N. I.; Kazakova, O. B.; Lopatina, T. V.; Smirnova, I. E.; Giniyatullina, G. V.; Baikova, I. P.; Kataev, V. E. Eur. J. Med. Chem. 2018, 143, 464. doi: S0223-5234(17)30938-8 pmid: 29202408
	(f) Chen, D. Y. K.; Pouwer, R. H.; Richard, J. A. Chem. Soc. Rev. 2012, 41, 4631. pmid: 29202408
	(g) Talele, T. T. J. Med. Chem. 2016, 59, 8712. pmid: 29202408
[2]	(a) Schneider, T. F.; Kaschel, J.; Werz, D. B. Angew. Chem., Int. Ed. 2014, 53, 5504. pmid: 28052543
	(b) Cavitt, M. A.; Phun, L. H.; France, S. Chem. Soc. Rev. 2014, 43, 804. pmid: 28052543
	(c) Braunschweig, H.; Dewhurst, R. D.; Ewing, W. C.; Kuntze‐ Fechner, M. W.; Schäfer, M. Chem.-Eur. J. 2017, 23, 5953. doi: 10.1002/chem.201605514 pmid: 28052543
	(d) Pilsl, L. K. A.; Ertl, T.; Reiser, O. Org. Lett. 2017, 19, 2754. pmid: 28052543
	(e) Ricci, L.; Sernissi, L.; Scarpi, D.; Bianchini, F.; Contini, A.; Occhiato, E. G. Org. Biomol. Chem. 2017, 15, 6826. pmid: 28052543
	(f) Yuan, C.; Du, B.; Yang, L.; Liu, B. J. Am. Chem. Soc. 2013, 135, 9291. pmid: 28052543
[3]	(a) Poudel, D. P.; Pokhrel, A.; Tak, R. K.; Shankar, M.; Giri, R. S. Science 2023, 381, 545.
	(b) Chen, Z. L.; Xie, Y.; Xuan, J. Eur. J. Org. Chem. 2022, e202201066.
	(c) Ebner, C.; Carreira, E. M. Chem. Rev. 2017, 117, 11651.
[4]	(a) Wu, W.; Lin, Z.; Jiang, H. Org. Biomol. Chem. 2018, 16, 7315. pmid: 26173173
	(b) Lebel, H.; Marcoux, J.-F.; Molinaro, C.; Charette, A. B. Chem. Rev. 2003, 103, 977. pmid: 26173173
	(c) Thankachan, A. P.; Sindhu, K. S.; Krishnan, k. k.; Anilkumar, G. Org. Biomol. Chem. 2015, 13, 8780. doi: 10.1039/c5ob01088h pmid: 26173173
	(d) Bos, M.; Posiion, T.; Pannecoucke, X.; Charette, A. B. Chem. Eur. J. 2017, 23, 4950. pmid: 26173173
	(e) Dian, L.; Marek, I. Chem. Rev. 2018, 118, 8415. pmid: 26173173
[5]	(a) Qian, D.; Zhang, J. Chem. Soc. Rev. 2015, 44, 677.
	(b) Calò, F. P.; Zimmer, A.; Bistoni, G.; Fürstner, A. J. Am. Chem. Soc. 2022, 144, 7465.
	(c) Empel, C.; Jana, S.; Koenigs, E. M. Molecules 2020, 25, 880.
[6]	(a) Chandgude, A. L.; Ren, X.; Fasan, R. J. Am. Chem. Soc. 2019, 141, 9145. doi: 10.1021/jacs.9b02700 pmid: 31099569
	(b) Shen, J. J.; Zhu, S. F.; Cai, Y.; Xu, H.; Xie, X. L.; Zhou, Q. L. Angew. Chem., Int. Ed. 2014, 53, 13188. pmid: 31099569
	(c) Simmons, H. E.; Smith, R. D. J. Am. Chem. Soc. 1959, 81, 4256. pmid: 31099569
[7]	(a) Li, A.-H.; Dai, L.-X.; Aggarwal, V. K. Chem. Rev. 1997, 97, 2341.
	(b) Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1965, 87, 1353.
[8]	(a) Ni, J.; Xia, X.; Zheng, W.-F.; Wang, Z. J. Am. Chem. Soc. 2022, 144, 7889.
	(b) Kulinkovich, O. G.; Sviridov, S. V.; Vasilevski, D. A. Synthesis 1991, 1991, 234.
[9]	(a) Zhan, G.; Shi, M.-L.; He, Q.; Lin, W.-J.; Outang, Q.; Du, W.; Chen, Y.-C. Angew. Chem., Int. Ed. 2016, 55, 2147
	(b) Rueping, M.; Sundén, H.; Hubenera, L.; Sugiono, E. Chem. Commun. 2012, 48, 2201.
	(c) Shim, S. Y.; Kim, J. Y.; Nam, M.; Hwang, G.-S.; Ryu, D. H. Org. Lett. 2016, 18, 160.

Entry	Solvent	Base	Catalyst (equiv.)	Oxidant (equiv.)	Temperature/℃	Time/h	Yield ^b/%
1	EtOH	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	65
2	EtOH	K₂CO₃	CuI (0.1)	TBHP (2.0)	Reflux	0.5	16
3	EtOH	K₂CO₃	NaI (0.1)	TBHP (2.0)	Reflux	0.5	4
4	EtOH	K₂CO₃	KI (0.1)	TBHP (2.0)	Reflux	0.5	6
5	EtOH	K₂CO₃	NH₄I (0.1)	TBHP (2.0)	Reflux	0.5	Trace
6	EtOH	K₂CO₃	CaI₂ (0.1)	TBHP (2.0)	Reflux	0.5	Trace
7	EtOH	K₂CO₃	MgI₂ (0.1)	TBHP (2.0)	Reflux	0.5	N.R.
8	EtOH	K₂CO₃	—	TBHP (2.0)	Reflux	0.5	N.R
9	EtOH	K₂CO₃	I₂ (0.5)	TBHP (2.0)	Reflux	0.5	69
10	EtOH	K₂CO₃	I₂ (1.0)	TBHP (2.0)	Reflux	0.5	70
11	EtOH	—	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	N.R
12	EtOH	Cs₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	Trace
13	EtOH	Et₃N	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	Trace
14	EtOH	Piperidine	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	11
15	EtOH	KOH	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	43
16	EtOH	K₂CO₃	I₂ (0.1)	—	Reflux	0.5	N.R.
17	EtOH	K₂CO₃	I₂ (0.1)	DTBP (2.0)	Reflux	0.5	N.R.
18	EtOH	K₂CO₃	I₂ (0.1)	H₂O₂ (2.0)	Reflux	0.5	Trace
19	EtOH	K₂CO₃	I₂ (0.1)	O₂	Reflux	0.5	Trace
20	EtOH	K₂CO₃	I₂ (0.1)	TBHP (1.0)	Reflux	0.5	30
21	EtOH	K₂CO₃	I₂ (0.1)	TBHP (4.0)	Reflux	0.5	61
22	CHCl₃	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	26
23	acetone	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	52
24	Cyclohexane	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	37
25	MeCN	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	82
26	MeCN	K₂CO₃	I₂ (0.1)	TBHP (2.0)	25	0.5	43
27	MeCN	K₂CO₃	I₂ (0.1)	TBHP (2.0)	50	0.5	69

Entry	Solvent	Base	Catalyst (equiv.)	Oxidant (equiv.)	Temperature/℃	Time/h	Yield ^b/%
1	EtOH	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	65
2	EtOH	K₂CO₃	CuI (0.1)	TBHP (2.0)	Reflux	0.5	16
3	EtOH	K₂CO₃	NaI (0.1)	TBHP (2.0)	Reflux	0.5	4
4	EtOH	K₂CO₃	KI (0.1)	TBHP (2.0)	Reflux	0.5	6
5	EtOH	K₂CO₃	NH₄I (0.1)	TBHP (2.0)	Reflux	0.5	Trace
6	EtOH	K₂CO₃	CaI₂ (0.1)	TBHP (2.0)	Reflux	0.5	Trace
7	EtOH	K₂CO₃	MgI₂ (0.1)	TBHP (2.0)	Reflux	0.5	N.R.
8	EtOH	K₂CO₃	—	TBHP (2.0)	Reflux	0.5	N.R
9	EtOH	K₂CO₃	I₂ (0.5)	TBHP (2.0)	Reflux	0.5	69
10	EtOH	K₂CO₃	I₂ (1.0)	TBHP (2.0)	Reflux	0.5	70
11	EtOH	—	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	N.R
12	EtOH	Cs₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	Trace
13	EtOH	Et₃N	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	Trace
14	EtOH	Piperidine	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	11
15	EtOH	KOH	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	43
16	EtOH	K₂CO₃	I₂ (0.1)	—	Reflux	0.5	N.R.
17	EtOH	K₂CO₃	I₂ (0.1)	DTBP (2.0)	Reflux	0.5	N.R.
18	EtOH	K₂CO₃	I₂ (0.1)	H₂O₂ (2.0)	Reflux	0.5	Trace
19	EtOH	K₂CO₃	I₂ (0.1)	O₂	Reflux	0.5	Trace
20	EtOH	K₂CO₃	I₂ (0.1)	TBHP (1.0)	Reflux	0.5	30
21	EtOH	K₂CO₃	I₂ (0.1)	TBHP (4.0)	Reflux	0.5	61
22	CHCl₃	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	26
23	acetone	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	52
24	Cyclohexane	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	37
25	MeCN	K₂CO₃	I₂ (0.1)	TBHP (2.0)	Reflux	0.5	82
26	MeCN	K₂CO₃	I₂ (0.1)	TBHP (2.0)	25	0.5	43
27	MeCN	K₂CO₃	I₂ (0.1)	TBHP (2.0)	50	0.5	69