Manganese-Catalyzed Ring-Opening C—C Bond Fluorination of Cyclobutanols

doi:10.6023/cjoc202401031

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (7): 2333-2340.DOI: 10.6023/cjoc202401031 Previous Articles Next Articles

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锰催化环丁醇开环的C—C键氟化反应

王丽梅^a, 刘晓圆^a, 昝金成^c, 孙书涛^b, 刘磊^b^,^*(), 李伟^a^,^*(), 刘希功^b^,^*()

a 山东中医药大学药学院济南 250355
b 山东大学化学与化工学院济南 250100
c 山东第一医科大学药学院(药物研究所) 济南 250117

收稿日期:2024-01-26 修回日期:2024-03-15 发布日期:2024-03-28
作者简介:
† 共同第一作者.
基金资助:
国家自然科学基金(92156008); 国家自然科学基金(22161142016); 山东省泰山学者计划和山东省自然科学基金(ZR2020QB018)

Manganese-Catalyzed Ring-Opening C—C Bond Fluorination of Cyclobutanols

Limei Wang^a, Xiaoyuan Liu^a, Jincheng Zan^c, Shutao Sun^b, Lei Liu^b(), Wei Li^a(), Xigong Liu^b()

a School of Pharmacy, Shandong University of Traditional Chinese Medicine, Jinan 250355
b School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100
c School of Pharmaceutical Sciences & Institute of Materia Medica, Shandong First Medical University, Jinan 250117

Received:2024-01-26 Revised:2024-03-15 Published:2024-03-28
Contact: * E-mail: leiliu@sdu.edu.cn;liwei6911@163.com;xigongliu@sdu.edu.cn
About author:
† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(92156008); National Natural Science Foundation of China(22161142016); Taishan Scholar Program at Shandong Province and the Natural Science Foundation of Shandong Province(ZR2020QB018)

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Abstract

Manganese-catalyzed C—C bond cleavage of cyclobutanols has attracted great attention due to the high abundance and cheap and eco-friendly behaviour. A manganese-catalyzed ring-opening C—C bond fluorination of cyclobutanols is reported. Under mild conditions, the reaction provides a straightforward access to γ-fluorinated ketones using 10 mol% Mn(OAc)₂ as catalyst and electrophilic fluorination reagent, which was generated in situ from HF•Et₃N and PhIO, as fluorine source. The reaction has an excellent functional-group tolerance and displays a broad substrate scope, affording the corresponding products in 50%~76% yields.

Key words: manganese catalysis, C—C bond functionalization, cyclobutanol, fluorination, γ-fluorinated ketone

Cite this article

Limei Wang, Xiaoyuan Liu, Jincheng Zan, Shutao Sun, Lei Liu, Wei Li, Xigong Liu. Manganese-Catalyzed Ring-Opening C—C Bond Fluorination of Cyclobutanols[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2333-2340.

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References 10

[1]	(a) Müller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881. pmid: 31588625
	(b) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320. pmid: 31588625
	(c) O’Hagan, D. J. Fluorine Chem. 2010, 131, 1071. pmid: 31588625
	(d) Johnson, B. M.; Shu, Y.-Z.; Zhuo, X.; Meanwell, N. A. J. Med. Chem. 2020, 63, 6315. pmid: 31588625
	(e) Cheng, M.; Guo, C.; Gross, M. L. Angew. Chem., Int. Ed. 2020, 59, 5880. doi: 10.1002/anie.201907662 pmid: 31588625
	(f) Ogawa, Y.; Tokunaga, E.; Kobayashi, O.; Hirai, K.; Shibata, N. iScience 2020, 23, 101467. pmid: 31588625
	(g) Li, Y.; Dai, M.; Wang, L.; Wang, G. J. Ethnopharmacol. 2021, 269, 113749. pmid: 31588625
	(h) Wang, L.; Wang, P.; Wang, D.; Tao, M.; Xu, W. Nat. Prod. Commun. 2020, 15, 20912088. pmid: 31588625
	(i) Song, A.; Ding, T.; Wei, N.; Yang, J.; Ma, M.; Zheng, S.; Jin, H. Toxicol. Appl. Pharmacol. 2023, 472, 116574. pmid: 31588625
[2]	(a) Thayer, A. M. Chem. Eng. News 2006, 84, 15. pmid: 22213395
	(b) Ametamey, S. M.; Honer, M.; Schubiger, P. A. Chem. Rev. 2008, 108, 1501. doi: 10.1021/cr0782426 pmid: 22213395
	(c) Littich, R.; Scott, P. J. H. Angew. Chem., Int. Ed. 2012, 51, 1106. doi: 10.1002/anie.201106785 pmid: 22213395
	(d) Wang, J.; Sánchez-Roselló, M.; Aceña, J. L.; del Pozo, C.; Sorochinsky, A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Chem. Rev. 2014, 114, 2432. pmid: 22213395
	(e) de la Torre, B. G.; Albericio, F. Molecules 2021, 26, 627. pmid: 22213395
	(f) Wang, L.; Wang, N.; Qi, Y.; Sun, S.; Liu, X.; Li, W.; Liu, L. Chin. J. Org. Chem. 2020, 40, 3934. (in Chinese) pmid: 22213395
	(王琳, 王楠, 齐越, 孙书涛, 刘希功, 李伟, 刘磊, 有机化学, 2020, 40, 3934.) doi: 10.6023/cjoc202004027 pmid: 22213395
	(g) Wang, D.; Kan, L.; Ma, Y.; Liu, L. Chin. J. Org. Chem. 2021, 41, 3192. (in Chinese) pmid: 22213395
	(王东琳, 阚玲珑, 马玉道, 刘磊, 有机化学, 2021, 41, 3192.) doi: 10.6023/cjoc202104003 pmid: 22213395
	(h) Du, T.; Li, S.; He, Y.; Long, H.; Liu, X.; Li, H.-B.; Liu, L. Chin. J. Chem. 2022, 40, 1681. pmid: 22213395
	(i) Zang, L.; Xu, H.; Huang, C.; Wang, C.; Wang, R.; Chen, R.; Chen, Y.; Wang, L.; Wang, H. Recent Pat. Anticancer Drug Discov. 2022, 17, 145. pmid: 22213395
	(j) Hong, H.; Zou, Q.; Liu, Y.; Wang, S.; Shen, G.; Yan, X. ChemMedChem 2021, 16, 2381. pmid: 22213395
	(k) Wang, X.; Shen, C.; Wang, X.; Tang, J.; Wu, Z.; Huang, Y.; Shao, W.; Geng, K.; Xie, H.; Pu, Z. Chin. Med. 2023, 18, 112. pmid: 22213395
[3]	(a) O’Hagan, D. Chem. Soc. Rev. 2008, 37, 308. pmid: 29608052
	(b) Furuya, T.; Kamlet, A. S.; Ritter, T. Nature 2011, 473, 470. pmid: 29608052
	(c) Campbell, M. G.; Ritter, T. Chem. Rev. 2015, 115, 612. doi: 10.1021/cr500366b pmid: 29608052
	(d) Champagne, P. A.; Desroches, J.; Hamel, J.-D.; Vandamme, M.; Paquin, J.-F. Chem. Rev. 2015, 115, 9073. pmid: 29608052
	(e) Yerien, D. E.; Bonesi, S.; Postigo, A. Org. Biomol. Chem. 2016, 14, 8398. pmid: 29608052
	(f) Zhu, Y.; Han, J.; Wang, J.; Shibata, N.; Sodeoka, M.; Soloshonok, V. A.; Coelho, J. A. S.; Toste, F. D. Chem. Rev. 2018, 118, 3887. doi: 10.1021/acs.chemrev.7b00778 pmid: 29608052
	(g) Szpera, R.; Moseley, D. F. J.; Smith, L. B.; Sterling, A. J.; Gouverneur, V. Angew. Chem., Int. Ed. 2019, 58, 14824. pmid: 29608052
[4]	(a) Seiser, T.; Saget, T.; Tran, D. N.; Cramer, N. Angew. Chem., Int. Ed. 2011, 50, 7740. pmid: 25266824
	(b) Souillart, L.; Parker, E.; Cramer, N. Top. Curr. Chem. 2014, 346, 163. doi: 10.1007/128_2013_505 pmid: 25266824
	(c) Marek, I.; Masarwa, A.; Delaye, P.-O.; Leibeling, M. Angew. Chem., Int. Ed. 2015, 54, 414. doi: 10.1002/anie.201405067 pmid: 25266824
	(d) Ren, R.; Zhu, C. Synlett 2016, 27, 1139. pmid: 25266824
	(e) Wu, X.; Zhu, C. Chem. Rec. 2018, 18, 587. pmid: 25266824
	(f) Yan, H.; Smith, G. S.; Chen, F.-E. Green Synth. Catal. 2022, 3, 219. pmid: 25266824
	(g) Sun, Y.; Yang, L.; Cheng, Y.; An, G.; Li, G. Chin. Chem. Lett. 2024, 35, 109250. pmid: 25266824
	(h) Zhai, S.; Qiu, S.; Yang, S.; Gao, X.; Feng, X.; Yun, C.; Han, N.; Niu, Y.; Wang, J.; Zhai, H. Chin. Chem. Lett. 2023, 34, 107657. pmid: 25266824
	(i) Wu, K.; Li, X.; Wang, W.; Huang, Y.; Jiang, Q.; Li, W.; Chen, Y.; Yang, Y.; Li, C. ACS Catal. 2022, 12, 4261. pmid: 25266824
	(j) Fang, L.; Jia, S.; Fan, S.; Zhu, J. Chem. Commun. 2023, 59, 10392. pmid: 25266824
[5]	(a) Zhao, H.; Fan, X.; Yu, J.; Zhu, C. J. Am. Chem. Soc. 2015, 137, 3490.
	(b) Ren, S.; Feng, C.; Loh, T.-P. Org. Biomol. Chem. 2015, 13, 5105.
	(c) Ishida, N.; Okumura, S.; Nakanishi, Y.; Murakami, M. Chem. Lett. 2015, 44, 821.
[6]	(a) Ren, R.; Wu, Z.; Xu, Y.; Zhu, C. Angew. Chem., Int. Ed. 2016, 55, 2866.
	(b) Ren, R.; Wu, Z.; Zhu, C. Chem. Commun. 2016, 52, 8160.
	(c) Wang, D.; Ren, R.; Zhu, C. J. Org. Chem. 2016, 81, 8043.
	(d) Allen, B. D. W.; Hareram, M. D.; Seastram, A. C.; McBride, T.; Wirth, T.; Browne, D. L.; Morrill, L. C. Org. Lett. 2019, 21, 9241.
	(e) Zhang, Y.-H.; Zhang, W.-W.; Zhang, Z.-Y.; Zhao, K.; Loh, T.-P. Org. Lett. 2019, 21, 5101.
	(f) Meyer, T.; Yin, Z.; Wu, X.-F. Tetrahedron Lett. 2019, 60, 864. doi: 10.1016/j.tetlet.2019.02.028
	(g) Lou, C.; Lv, L.; Li, Z. Adv. Synth. Catal. 2022, 364, 3743.
	(h) He, Y.; Du, C.; Han, J.; Zhu, C.; Xie, J. Chin. J. Chem. 2022, 40, 1546.
[7]	Lu, Y.-C.; West, J. G. ACS Catal. 2021, 11, 12721.
[8]	(a) Kitamura, T.; Kuriki, S.; Morshed, M. H.; Hori, Y. Org. Lett. 2011, 13, 2392. doi: 10.1021/ol200632d pmid: 29431440
	(b) Kitamura, T.; Muta, K. J. Org. Chem. 2014, 79, 5842. doi: 10.1021/jo500691b pmid: 29431440
	(c) Kitamura, T.; Mizuno, S.; Muta, K.; Oyamada, J. J. Org. Chem. 2018, 83, 2773. doi: 10.1021/acs.joc.7b03223 pmid: 29431440
	(d) Wang, L.; Kitamura, T.; Zhou, Y.; Butler, G.; Han, J.; Soloshonok, V. A. J. Fluorine Chem. 2020, 240, 109670. pmid: 29431440
[9]	(a) Ren, R.; Zhao, H.; Huan, L.; Zhu, C. Angew. Chem., Int. Ed. 2015, 54, 12692.
	(b) Huan, L.; Zhu, C. Org. Chem. Front. 2016, 3, 146.
	(c) Liu, W.; Huang, X.; Cheng, M.-J.; Nielsen, R. J.; Goddard, W. A., III; Groves, J. T. Science 2012, 337, 1322.
	(d) Huang, X.; Liu, W.; Hooker, J. M.; Groves, J. T. Angew. Chem., Int. Ed. 2015, 54, 5241.
[10]	(a) He, Y.; Tian, C.; An, G.; Li, G. Chin. Chem. Lett. 2024, 35, 108546.
	(b) Lv, X.; Cheng, Y.; Zong, Y.; Wang, Q.; An, G.; Wang, J.; Li, G. ACS Catal. 2023, 13, 7310.

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锰催化环丁醇开环的C—C键氟化反应

Manganese-Catalyzed Ring-Opening C—C Bond Fluorination of Cyclobutanols

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Entry	Catalyst	Oxidant	Solvent	Temperature/℃	Yield^b/%
1	Mn(OAc)₂•4H₂O	PhIO	DCE/H₂O (V∶V=1∶1)	60	61
2	Mn(OAc)₃	PhIO	DCE/H₂O (V∶V=1∶1)	60	45
3	Mn(OAc)₂	PhIO	DCE/H₂O (V∶V=1∶1)	60	76
4	Mn(acac)₂	PhIO	DCE/H₂O (V∶V=1∶1)	60	36
5	Mn(OAc)₂	PIDA	DCE/H₂O (V∶V=1∶1)	60	30
6	Mn(OAc)₂	PIFA	DCE/H₂O (V∶V=1∶1)	60	25
7	Mn(OAc)₂	IBX	DCE/H₂O (V∶V=1∶1)	60	35
8	Mn(OAc)₂	Other oxidant^c	DCE/H₂O (V∶V=1∶1)	60	<20
9	Mn(OAc)₂	PhIO	Acetonitrile/H₂O (V∶V=1∶1)	60	32
10	Mn(OAc)₂	PhIO	Toluene/H₂O (V∶V=1∶1)	60	<5
11	Mn(OAc)₂	PhIO	THF/H₂O (V∶V=1∶1)	60	<5
12	Mn(OAc)₂	PhIO	DCE/H₂O (V∶V=1∶2)	60	<5
13	Mn(OAc)₂	PhIO	DCE/H₂O (V∶V=2∶1)	60	<5
14	Mn(OAc)₂	PhIO	DCE	60	<5
15	Mn(OAc)₂	PhIO	DCE/H₂O (V∶V=1∶1)	25	<5
16	Mn(OAc)₂	PhIO	DCE/H₂O (V∶V=1∶1)	40	26
17	Mn(OAc)₂	PhIO	DCE/H₂O (V∶V=1∶1)	50	29
18	Mn(OAc)₂	PhIO	DCE/H₂O (V∶V=1∶1)	70	41