Difluorocarbene-Enabled Synthesis of 3-Substituted-2-oxoindoles from o-Vinylanilines

doi:10.6023/cjoc202210031

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (3): 1146-1156.DOI: 10.6023/cjoc202210031 Previous Articles Next Articles

Special Issue: 有机氟化学虚拟合辑；中国女科学家专辑

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二氟卡宾参与下从邻乙烯基苯胺出发构建3-取代吲哚酮类化合物

黄华^a, 李鑫^a, 苏建科^a, 宋秋玲^a^,^b^,^c^,^*()

a 华侨大学材料科学工程学院下一代物质转化研究所福建厦门 361021
b 中国科学院上海有机化学研究所金属有机化学国家重点实验室和有机氟化学重点实验室上海 200032
c 河南师范大学化学化工学院河南新乡 453007

收稿日期:2022-10-26 修回日期:2022-11-30 发布日期:2022-12-21
通讯作者: 宋秋玲
基金资助:
国家自然科学基金(21931013)

Difluorocarbene-Enabled Synthesis of 3-Substituted-2-oxoindoles from o-Vinylanilines

Hua Huang^a, Xin Li^a, Jianke Su^a, Qiuling Song^a^,^b^,^c()

a Institute of Next Generation Matter Transformation, College of Material Sciences Engineering, Huaqiao University, Xiamen, Fujian 361021
b State Key Laboratory of Organometallic Chemistry and Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
c School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007

Received:2022-10-26 Revised:2022-11-30 Published:2022-12-21
Contact: Qiuling Song
Supported by:
National Natural Science Foundation(21931013)

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Abstract

A novel transition-metal-free protocol for the synthesis of 1-alkyl-3-(2-oxo-2-aryl/alkyl-ethyl)indolin-2-ones is developed. This work reveals that oxoindole skeletons can be directly constructed from ortho-vinylanilines and commercially available halogenated difluoroalkyl reagents via a C—N cleavage/new C—N bonds and C—C bond formation cascade. This reaction portrays high efficiency and excellent functional group compatibility, and has great potential in the late-stage modifications of pharmaceutical molecules and natural products.

Key words: halo difluoro reagent, 3-substituted 2-oxindole, difluorocarbene

Cite this article

Hua Huang, Xin Li, Jianke Su, Qiuling Song. Difluorocarbene-Enabled Synthesis of 3-Substituted-2-oxoindoles from o-Vinylanilines[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1146-1156.

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References 11

[1]	(a) Peng, Y.; Keenan, S. M.; Welsh, W. J. J. Mol. Graphics Modell. 2005, 24, 72. doi: 10.1016/j.jmgm.2005.06.002 pmid: 15481979
	(b) Bhattacharjee, A. K.; Geyer, J. A.; Woodard, C. L.; Kathcart, A. K.; Nichols, D. A.; Prigge, S. T.; Li, Z.; Mott, B. T.; Waters, N. C. J. Med. Chem. 2004, 47, 5418. pmid: 15481979
	(c) Woodard, C. L.; Li, Z.; Kathcart, A. K.; Terrell, J.; Gerena, L.; Lopez-Sanchez, M.; Kyle, D. E.; Bhattacharjee, A. K.; Nichols, D. A.; Ellis, W.; Prigge, S. T.; Geyer, J. A.; Waters, N. C. J. Med. Chem. 2003, 46, 3877. doi: 10.1021/jm0300983 pmid: 15481979
	(d) Klöck, C.; Jin, X.; Choi, K.; Khosla, C.; Madrid, P. B.; Spencer, A.; Raimundo, B. C.; Boardman, P.; Lanza, G.; Griffin, J. H. Bioorg. Med. Chem. Lett. 2011, 21, 2692. doi: 10.1016/j.bmcl.2010.12.037 pmid: 15481979
	(e) Matheson, C. J.; Casalvieri, K. A.; Backos, D. S.; Minhajuddin, M.; Jordan, C. T.; Reigan, P. Eur. J. Med. Chem. 2020, 197, 112316. doi: 10.1016/j.ejmech.2020.112316 pmid: 15481979
	(f) Edupuganti, R.; Taliaferro, J. M.; Wang, Q.; Xie, X.; Cho, E. J.; Vidhu, F.; Ren, P.; Anslyn, E. V.; Bar-tholomeusz, C.; Dalby, K. N. Bioorg. Med. Chem. 2017, 25, 2609. doi: 10.1016/j.bmc.2017.03.018 pmid: 15481979
[2]	Yong, S. R.; Ung, A. T.; Pyne, S. G.; Skelton, B. W.; White, A. H. Tetrahedron Lett. 2007, 63, 5579. doi: 10.1016/j.tet.2007.04.028
[3]	Yasuda, D.; Takahashi, K.; Ohe, T.; Nakamura, S.; Mashino, T. Bioorg. Med. Chem. 2013, 21, 7709. doi: 10.1016/j.bmc.2013.10.021
[4]	Lai, J. Y.; Cox, P. J.; Patel, R.; Sadiq, S.; Aldous, D. J.; Thurai- ratnam, S.; Smith, K.; Wheeler, D.; Jagpal, S.; Parveen, S.; Fenton, G.; Harrison, T. K.; McCarthy, C.; Bamborough, P. Bioorg. Med. Chem. 2003, 13, 3111. doi: 10.1016/S0960-894X(03)00658-9
[5]	(a) Saito, N.; Kanno, Y.; Yamashita, N.; Degawa, M.; Yoshinari, K.; Nemoto, K. Biol. Pharm. Bull. 2021, 44, 571. doi: 10.1248/bpb.b20-00961 pmid: 23716882
	(b) Sano, M.; Ichimaru, Y.; Kurita, M.; Hayashi, E.; Homma, T.; Saito, H.; Masuda, S.; Nemoto, N.; Hemmi, A.; Suzuki, T.; Miyairi, S.; Hao, H. Cancer Lett. 2017, 397, 72. doi: 10.1016/j.canlet.2017.03.031 pmid: 23716882
	(c) Xie, K.; Chen, R.; Chen, D.; Li, J.; Wang, R.; Yang, L.; Dai, J. Adv. Synth. Catal. 2017, 359, 603. doi: 10.1002/adsc.v359.4 pmid: 23716882
	(d) Huang, M.; Wang, L.; Zeng, S.; Qiu, Q.; Zou, Y.; Shi, M.; Xu, H.; Liang, L. Inflammation Res. 2017, 66, 433. doi: 10.1007/s00011-017-1027-5 pmid: 23716882
	(e) Otlowska, O.; Slebioda, M.; Kot-Wasik, A.; Karczewski, J.; SLiwka-KaszynSka, M. Molecules 2018, 23, 339. doi: 10.3390/molecules23020339 pmid: 23716882
	(f) Aouidate, A.; Ghaleb, A.; Ghamali, M.; Chtita, S.; Ousaa, A.; Choukrad, M.; Sbai, A.; Bouachrine, M.; Lakhlifi, T. Struct. Chem. 2018, 29, 1609. doi: 10.1007/s11224-018-1134-0 pmid: 23716882
	(g) Aourz, N.; Serruys, A. K.; Chabwine, J. N.; Balegamire, P. B.; Afrikanova, T.; Edrada-Ebel, R.; Grey, A. I.; Kamuhabwa, A. R.; Walrave, L.; Esguerra, C. V.; Leuven, F. V.; Witte, P. A. M. D.; Smolders, I.; Crawford, A. D. ACS Chem. Neurosci. 2019, 10, 1992. doi: 10.1021/acschemneuro.8b00281 pmid: 23716882
	(h) Xu, X.; Wei, Y.; Guo, Q.; Zhao, S.; Liu, Z.; Xiao, T.; Liu, Y.; Qiu, Y.; Hou, Y.; Zhang, G.; Wang, K. J. Pharmacol. Exp. Ther. 2018, 365, 624. doi: 10.1124/jpet.118.248351 pmid: 23716882
	(i) Nguyen, D. T.; Truong, G. N.; Vuong, V. T.; Van, T. N.; Manh, C. N.; Dao, C. T.; Thuy, T. D. T.; Van, C. L.; Khac, V. T. Chem. Pap. 2019, 73, 1083. doi: 10.1007/s11696-018-0659-4 pmid: 23716882
	(j) Thakur, R. K.; Joshi, P.; Upadhyaya, K.; Singh, K.; Sharma, G.; Shukla, S. K.; Tripathi, R.; Tripathi, R. P. Eur. J. Med. Chem. 2019, 162, 448. doi: S0223-5234(18)30962-0 pmid: 23716882
	(k) Tanaka, T.; Saito, H.; Miyairi, S.; Kobayashi, S. Biochem. Biophys. Res. Commun. 2021, 544, 15. doi: 10.1016/j.bbrc.2021.01.048 pmid: 23716882
	(l) Gupta, A. K.; Kalpana, S.; Malik, J. K. Indian J. Pharm. Sci. 2012, 74, 481. doi: 10.4103/0250-474X.108445 pmid: 23716882
	(m) Dawar, M.; Utreja, D.; Rani, R.; Kaur, K. Lett. Org. Chem. 2020, 17, 199. doi: 10.2174/1570178616666190724120308 pmid: 23716882
[6]	(a) Sohail, M.; Tanaka, F. Angew. Chem., Int. Ed. 2021, 60, 21256. doi: 10.1002/anie.202108734 pmid: 25575040
	(b) Vive-kanand, T.; Vinoth, P.; Agieshkumar, B.; Sampath, N.; Sudalai, A.; Menéndez, J. C.; Sridharan, V. Green Chem. 2015, 17, 3415. doi: 10.1039/C5GC00365B pmid: 25575040
	(c) Zhou, Z.; Wang, Z.; Zhou, Y.; Xiao, W.; Ouyang, Q.; Du, W.; Chen, Y. Nat. Chem. 2017, 9, 590. doi: 10.1038/nchem.2698 pmid: 25575040
	(d) Basu, S.; Mukhopadhyay, C. Eur. J. Org. Chem. 2018, 2018, 1496. doi: 10.1002/ejoc.v2018.12 pmid: 25575040
	(e) Parveen, I.; Khan, D.; Ahmed N. Eur. J. Org. Chem. 2019, 2019, 759. doi: 10.1002/ejoc.201801385 pmid: 25575040
	(f) Halskov, K. S.; Kniep, F.; Lauridsen, V. H.; Iversen, E. H.; Donslund, B. S.; Jørgensen K. A. J. Am. Chem. Soc. 2015, 137, 1685. doi: 10.1021/ja512573q pmid: 25575040
	(g) Prieto, L.; Sánchez-Díez, E.; Uria, U.; Reyes, E.; Carrillo, L.; Vicario, L. J. Adv. Synth. Catal. 2017, 359, 1678. doi: 10.1002/adsc.v359.10 pmid: 25575040
	(h) Faita, G.; Mella, M.; Righetti, P.; Tacconi, G. Tetrahedron 1994, 50, 10955. doi: 10.1016/S0040-4020(01)85706-9 pmid: 25575040
	(i) Zhao, B.; Du, D. Adv. Synth. Catal. 2019, 361, 3412. doi: 10.1002/adsc.v361.14 pmid: 25575040
	(j) Li, D.; Liu, K.; Jiang, Y.; Gu, Y.; Zhang, J.; Zhao, L. Org. Lett. 2018, 20, 1122. doi: 10.1021/acs.orglett.8b00045 pmid: 25575040
	(k) Fu, Y.; Hu, S.; Li, S.; Li, X. Synth. Commun. 2019, 49, 1067. doi: 10.1080/00397911.2019.1587779 pmid: 25575040
[7]	(a) Du, Y.; Li, J.; Chen, K.; Wu, C.; Zhou, Y.; Liu, H. J. Org. Chem. 2017, 13, 1342. pmid: 34021187
	(b) Biswas, P.; Mandal, S.; Guin, J. Org. Lett. 2020, 22, 4294. doi: 10.1021/acs.orglett.0c01336 pmid: 34021187
	(c) Fujita, S.; Imagawa, K.; Yamaguchi, S.; Yamasaki, J.; Yamazoe, S.; Mizugaki, T.; Mitsudome, T. Sci. Rep. 2021, 11, 10673. doi: 10.1038/s41598-021-89561-1 pmid: 34021187
[8]	(a) Ma, X.; Song, Q. Chem. Soc. Rev. 2020, 49, 9197. doi: 10.1039/D0CS00604A pmid: 31548670
	(b) Dilman, A. D.; Levin, V. V. Acc. Chem. Res. 2018, 51, 1272. doi: 10.1021/acs.accounts.8b00079 pmid: 31548670
	(c) Liang, H.; Liu, R.; Zhou, M.; Fu, Y.; Ni, C.; Hu, J. Org. Lett. 2020, 22, 7047. doi: 10.1021/acs.orglett.0c02688 pmid: 31548670
	(d) Smirnov, V. O.; Volodin, A. D.; Korlyukov, A. A.; Dilman, A. D. Angew. Chem.,Int. Ed. 2020, 59, 12428. doi: 10.1002/anie.v59.30 pmid: 31548670
	(e) Wang, Y.; Mu, S.; Li, X.; Song, Q. Chin. Chem. Lett. 2020, 33, 1511. doi: 10.1016/j.cclet.2021.08.089 pmid: 31548670
	(f) Ai, H.-J.; Ma, X.; Song, Q.; Wu, X.-F. Sci. China: Chem. 2021, 64, 1630. doi: 10.1007/s11426-021-1040-2 pmid: 31548670
	(g) Zhang, X.; Feng, Z.; Min, Q. Org. Lett. 2016, 18, 44. doi: 10.1021/acs.orglett.5b03206 pmid: 31548670
	(h) Zhang, X.; Feng, Z.; Min, Q.; Fu, X.; An, L. Nat. Chem. 2017, 9, 918. doi: 10.1038/nchem.2746 pmid: 31548670
	(i) Zhang, X.; Houk, K.; Fu, X.; Xue, X.; Zhang, X.; Xiao, Y.; Zhang, S.; Guo, Y. Nat. Chem. 2019, 11, 948. doi: 10.1038/s41557-019-0331-9 pmid: 31548670
[9]	Hu, J.; Han, X.; Yuan, Y.; Shi, Z. Angew. Chem., Int. Ed. 2017, 56, 13342.
[10]	(a) Su, J.; Ma, X.; Ou, Z.; Song, Q. ACS Cent. Sci. 2020, 6, 1819. doi: 10.1021/acscentsci.0c00779
	(b) Zhang, G.; Shi, Q.; Hou, M.; Yang, K.; Wang, S.; Wang, S.; Li, W.; Li, C.; Qiu, J.; Xu, H.; Zhou, L.; Wang, C.; Li, S.-J.; Lan, Y.; Song, Q. CCS Chem. 2021, 3, 1613.
	(c) Su, J.; Hu, X.; Huang, H.; Guo, Y.; Song, Q. Nat. Commun. 2021, 12, 4986. doi: 10.1038/s41467-021-25313-z
	(d) Deng, S.; Song, Q. Chem. Sci. 2019, 10, 6828. doi: 10.1039/C9SC01333D
	(e) Ma, X.; Zhou, Y.; Song, Q. Org. Lett. 2018, 20, 4777. doi: 10.1021/acs.orglett.8b01888
	(f) Ma, X.; Mai, S.; Zhou, Y.; Cheng, G.-J.; Song, Q. Chem. Commun. 2018, 54, 8960. doi: 10.1039/C8CC04298E
	(g) Ma, X.; Su, J.; Zhang, X.; Song, Q. iScience 2019, 19, 1. doi: 10.1016/j.isci.2019.07.005
	(h) Kim, Y.; Heo, J.; Kim, D.; Chang, S.; Seo, S. Nat. Commun. 2020, 11, 4761. doi: 10.1038/s41467-020-18557-8
	(i) Mita, T., Harabuchi, Y.; Maeda, S. Chem. Sci. 2020, 11, 7569. doi: 10.1039/D0SC02089C
	(j) Nawrot, E.; Joñczyk, A. J. Org. Chem. 2007, 72, 10258. doi: 10.1021/jo701735n
	(k) Ma, X.; Huang, H.; Su, J.; Song, Z.; Tamaki, N.; Song, Q. Chin. J. Chem. 2020, 38, 63. doi: 10.1002/cjoc.v38.1
	(l) Sheng, H.; Su, J.; Li, X.; Song, Q. CCS Chem. 2022, 4, 3820. doi: 10.31635/ccschem.022.202101576
[11]	(a) Verniest, G.; Colpaert, F.; Hende, E. V.; Kimpe, N. D. J. Org. Chem. 2007, 72, 8569. pmid: 23355490
	(b) Gilman, H.; Yale, H. L. J. Am. Chem. Soc. 1950, 72, 3646. doi: 10.1021/ja01164a090 pmid: 23355490
	(c) Hende, E. V.; Verniest, G.; Surmont, R.; Kimpe, N. D. Org. Lett. 2007, 9, 2935. pmid: 23355490
	(d) Eisenstein, O.; Milani, J.; Perutz, R. N. Chem. Rev. 2017, 117, 8710. doi: 10.1021/acs.chemrev.7b00163 pmid: 23355490
	(e) Whittlesey, M. K.; Peris, E. ACS Catal. 2014, 4, 3152. doi: 10.1021/cs500887p pmid: 23355490
	(f) Kuehnel, M. F.; Lentz, D.; Braun, T. Angew. Chem., Int. Ed. 2013, 52, 3328. doi: 10.1002/anie.201205260 pmid: 23355490
	(g) Lv, H.; Cai, Y.-B.; Zhang, J.-L. Angew. Chem., Int. Ed. 2013, 52, 3203. doi: 10.1002/anie.201208364 pmid: 23355490

Entry	Base	[∶CF₂]	Solvent	T/℃	Yield^b/%
1	K₂CO₃	2a	CH₃CN	90	76
2	KOH	2a	CH₃CN	90	45
3	Na₂CO₃	2a	CH₃CN	90	61
4	Na₃PO₄	2a	CH₃CN	90	56
5	K₃PO₄	2a	CH₃CN	90	93 (90^c)
6	K₃PO₄	2a	THF	90	15
7	K₃PO₄	2a	DME	90	Trace
8	K₃PO₄	2a	Toluene	90	n.r.
9	K₃PO₄	2b	CH₃CN	90	88
10	K₃PO₄	2c	CH₃CN	90	66
11	K₃PO₄	2d	CH₃CN	90	Trace
12	K₃PO₄	2e	CH₃CN	90	49
13	K₃PO₄	2a	CH₃CN	80	81
14	K₃PO₄	2a	CH₃CN	100	93
15	K₃PO₄	2a	CH₃CN	110	88

Entry	Base	[∶CF₂]	Solvent	T/℃	Yield^b/%
1	K₂CO₃	2a	CH₃CN	90	76
2	KOH	2a	CH₃CN	90	45
3	Na₂CO₃	2a	CH₃CN	90	61
4	Na₃PO₄	2a	CH₃CN	90	56
5	K₃PO₄	2a	CH₃CN	90	93 (90^c)
6	K₃PO₄	2a	THF	90	15
7	K₃PO₄	2a	DME	90	Trace
8	K₃PO₄	2a	Toluene	90	n.r.
9	K₃PO₄	2b	CH₃CN	90	88
10	K₃PO₄	2c	CH₃CN	90	66
11	K₃PO₄	2d	CH₃CN	90	Trace
12	K₃PO₄	2e	CH₃CN	90	49
13	K₃PO₄	2a	CH₃CN	80	81
14	K₃PO₄	2a	CH₃CN	100	93
15	K₃PO₄	2a	CH₃CN	110	88

二氟卡宾参与下从邻乙烯基苯胺出发构建3-取代吲哚酮类化合物

Difluorocarbene-Enabled Synthesis of 3-Substituted-2-oxoindoles from o-Vinylanilines

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[1]	Zhi Tu, Jinsheng Yu, Jian Zhou. Synthesis of (Bromodifluoromethyl)trimethylsilane and Its Applications in Organic Synthesis [J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3491-3507.
[2]	Qin Wenbing, Chen Jiayi, Xiong Wei, Liu Guokai. Recent Advance in Development and Application of Electrophilic Difluoromethylating Reagents [J]. Chinese Journal of Organic Chemistry, 2020, 40(10): 3177-3195.
[3]	Wang Weiqiang, Yu Qinwei, Zhang Qian, Li Jiangwei, Hui Feng, Yang Jianming, Lü Jian. Recent Progress on Difluoromethylation Methods [J]. Chin. J. Org. Chem., 2018, 38(7): 1569-1585.