Synthesis of γ-Carbolinone Derivatives via Manganese(III)-Promoted Tandem Phosphinoylation/Cyclization of Activated Alkenes with Phosphites

doi:10.6023/cjoc202509023

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (3): 1078-1086.DOI: 10.6023/cjoc202509023 Previous Articles Next Articles

ARTICLES

锰促进活化烯烃与亚磷酸酯串联磷酰化/环化反应合成γ-咔啉酮衍生物

印丘梅, 刘佳乐, 邓世强, 黄嘉明, 蒋洁, 唐裕才^*()

湖南文理学院化学与材料工程学院电镀废水回用技术湖南省工程研究中心电镀废水回用技术湖南省工程研究中心湖南常德 415000

收稿日期:2025-09-19 修回日期:2025-11-04 发布日期:2025-11-12
基金资助:
湖南省教育厅优秀科学研究项目(23B0650); 湖南文理学院重点项目(24ZZ02); 常德市科技创新指导性计划(2025ZD124)

Synthesis of γ-Carbolinone Derivatives via Manganese(III)-Promoted Tandem Phosphinoylation/Cyclization of Activated Alkenes with Phosphites

Qiumei Yin, Jiale Liu, Shiqiang Deng, Jiaming Huang, Jie Jiang, Yucai Tang^*()

Engineering Research Center of Hunan Province for Recycling Technology of Electroplating Wastewater, College of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde, Hunan 415000

Received:2025-09-19 Revised:2025-11-04 Published:2025-11-12
Contact: *E-mail: yctang1009@163.com
Supported by:
Scientific Research Foundation of Hunan Provincial Education Department(23B0650); Key Research Project of Hunan University of Arts and Sciences(24ZZ02); Technology Innovation and Development Guidance Program of Changde City(2025ZD124)

1. .pdf(5339KB)

Abstract

A manganese(III)-promoted tandem phosphinoylation/cyclization of activated alkenes with phosphites to synthesize γ-carbolinone derivatives has been developed. The present method exhibits excellent compatibility with various N-acryloyl-1H-indole-3-carboxamides and phosphites, and is easy to scale up, providing various γ-carbolinone derivatives in moderate to good yields.

Key words: manganese, alkene, phosphite, phosphinoylation/cyclization, γ-carbolinone

Cite this article

Qiumei Yin, Jiale Liu, Shiqiang Deng, Jiaming Huang, Jie Jiang, Yucai Tang. Synthesis of γ-Carbolinone Derivatives via Manganese(III)-Promoted Tandem Phosphinoylation/Cyclization of Activated Alkenes with Phosphites[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1078-1086.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

References 16

[1]	(a) Somei, M.; Yamada, F. Nat. Prod. Rep. 2005, 22, 73. doi: 10.1039/b316241a pmid: 36048958
	(b) Doody, R. S.; Gavrilova, S. I.; Sano, M.; Thomas, R. G.; Aisen, P. S.; Bachurin, S. O.; Seely, L.; Hung, D. Lancet 2008, 372, 207. doi: 10.1016/S0140-6736(08)61074-0 pmid: 36048958
	(c) Stempel, E.; Gaich, T. Acc. Chem. Res. 2016, 49, 2390. doi: 10.1021/acs.accounts.6b00265 pmid: 36048958
	(d) Singh, P. T.; Singh, M. O. Med. Chem. 2018, 18, 9. doi: 10.1021/jm00235a002 pmid: 36048958
	(e) Wan, Y.; Li, Y.; Yan, C.; Yan, M.; Tang, Z. Eur. J. Med. Chem. 2019, 183, 111691. doi: 10.1016/j.ejmech.2019.111691 pmid: 36048958
	(f) Reisenbauer, J. C.; Green, O.; Franchino, A.; Finkelstein, P.; Morandi, B. Science 2022, 377, 1104. doi: 10.1126/science.add1383 pmid: 36048958
	(g) Lu, Y.-H.; Wu, C.; Hou, J.-C.; Wu, Z.-L.; Zhou, M.-H.; Huang, X.-J.; He, W.-M. ACS Catal. 2023, 13, 13071. doi: 10.1021/acscatal.3c02268 pmid: 36048958
	(h) Song, H.; Jiang, J.; Wu, C.; Hou, J.; Lu, Y.; Wang, K.; Yang, T.; He, W.-M. Green Chem. 2023, 25, 3292. doi: 10.1039/D2GC04843D pmid: 36048958
	(i) Gui, Q.; Wang, B.; Zhu, S.; Li, F.; Zhu, M.; Yi, M.; Yu, J.; Wu, Z.; He, W.-M. Green Chem. 2021, 23, 4430. doi: 10.1039/D1GC01017D pmid: 36048958
	(j) Peng, Q.; Jiang, J.; Liao, Z.; Wu, Z.; Ou, L.; Dai, H.; Peng, J.; He, W.-M. ACS Sustainable Chem. Eng. 2025, 13, 10971. doi: 10.1021/acssuschemeng.5c03350 pmid: 36048958
[2]	(a) Sun, J.; Lou, H.; Dai, S.; Xu, H.; Zhao, F.; Liu, K. Phytochemistry 2008, 69, 1405. doi: 10.1016/j.phytochem.2008.01.008 pmid: 27237590
	(b) Sravanthi, T. V.; Manju, S. L. Eur. J. Pharm. Sci. 2016, 91, 1. doi: 10.1016/j.ejps.2016.05.025 pmid: 27237590
	(c) Dorababu, A. RSC Med. Chem. 2020, 11, 1335. doi: 10.1039/d0md00288g pmid: 27237590
	(d) Zhu, Y.; Zhao, J.; Luo, L.; Gao, Y.; Bao, H.; Li, P.; Zhang, H. Eur. J. Med. Chem. 2021, 223, 113665. doi: 10.1016/j.ejmech.2021.113665 pmid: 27237590
	(e) Ji, H.; Luo, Q.; Wang, K.; Ouyang, W.; Li, H.; He, W.-M. Green Chem. 2023, 25, 7983. doi: 10.1039/D3GC02575F pmid: 27237590
	(f) Wu, Y.; Chen, J.; Ning, J.; Jiang, X.; Deng, J.; Deng, Y.; Xu, R.; He, W.-M. Green Chem. 2021, 23, 3950. doi: 10.1039/D1GC00562F pmid: 27237590
	(g) Wen, Y.; Hou, J.; Zhou, Q.; Wang, S.; Jiang, J.; Yang, Z.; Zhu, H.; Wang, Z.; He, W.-M. Chin. Chem. Lett. 2025, 36, 111795. doi: 10.1016/j.cclet.2025.111795 pmid: 27237590
	(h) Peng, Q.; Li, N.; Hou, J.; He, C.; Yang, Y.; Zhuang, C.; Ou, L.; Yuan, M.; He, W.-M. Chin. Chem. Lett. 2025, 36, 111402. doi: 10.1016/j.cclet.2025.111402 pmid: 27237590
[3]	(a) Cincinelli, R.; Cassinelli, G.; Dallavalle, S.; Lanzi, C.; Merlini, L.; Botta, M.; Tuccinardi, T.; Martinelli, A.; Penco, S.; Zunino, F. J. Med. Chem. 2008, 51, 7777. doi: 10.1021/jm8007823 pmid: 19053769
	(b) Fedorov, O.; Huber, K.; Eisenreich, A.; Filippakopoulos, P.; King, O.; Bullock, A. N.; Szklarczyk, D.; Jensen, L. J.; Fabbro, D.; Trappe, J.; Rauch, U.; Bracher, F.; Knapp, S. Chem. Biol. 2011, 18, 67. doi: 10.1016/j.chembiol.2010.11.009 pmid: 19053769
[4]	Giorgetti, A.; Brunetti, P.; Haschimi, B.; Pulver, B.; Pascali, J. P.; Riedel, J.; Auwärter, V. Drug Test. Anal. 2024, 17, 882. doi: 10.1002/dta.3791 pmid: 39218806
[5]	(a) Abou-Gharbia, M. A. US 4748247, 1988.
	(b) Wang, Z.; Li, L.WO 2013/078544, 2013.
[6]	Shi, Z.; Cui, Y.; Jiao, N. Org. Lett. 2010, 12, 2908. doi: 10.1021/ol1007839
[7]	Mita, T.; Ishii, S.; Higuchi, Y.; Sato, Y. Org. Lett. 2018, 20, 7603. doi: 10.1021/acs.orglett.8b03337
[8]	Guha, S.; Gadde, S.; Kumar, N.; Black, D. S.; Sen, S. J. Org. Chem. 2021, 86, 5234. doi: 10.1021/acs.joc.1c00141
[9]	Yang, D. Y.; Liu, L.; Gu, J. Y.; He, Y. H.; Guan, Z. J. Org. Chem. 2021, 86,18042.
[10]	Luo, D.; Wang, Q.; Liu, J.; Mei, H.; Han, J. Org. Biomol. Chem. 2025, 23, 1309. doi: 10.1039/D4OB01703J
[11]	Du, Q.; Pan, R.; Chen, Y.; Tang, Y. RSC Adv. 2025, 15, 216. doi: 10.1039/D4RA08000A
[12]	(a) He, H. W. Phosphorus, Sulfur Silicon Relat. Elem. 2008, 183, 266. doi: 10.1080/10426500701734232 pmid: 17091932
	(b) Cui, S.; Zhang, Y.; Wu, Q. Chem. Sci. 2013, 4, 3421. doi: 10.1039/c3sc51424b pmid: 17091932
	(c) Queffélec, C.; Petit, M.; Janvier, P.; Knight, D. A.; Bujoli, B. Chem. Rev. 2012, 112, 3777. doi: 10.1021/cr2004212 pmid: 17091932
	(d) Baumgartner, T.; Réau, R. Chem. Rev. 2006, 106, 4681. doi: 10.1021/cr040179m pmid: 17091932
	(e) Wei, C.-C.; Kong, Y.-Y.; Hua, X.; Li, G.-Q.; Zheng, S.-L.; Cheng, M.-H.; Wang, P.; Miao, C.-Y. Br. J. Pharmacol. 2017, 174, 3823. doi: 10.1111/bph.v174.21 pmid: 17091932
[13]	(a) Moriarty, E.; Carr, M.; Bonham, S.; Carty, M. P.; Aldabbagh, F. Eur. J. Med. Chem. 2010, 45, 3762. doi: 10.1016/j.ejmech.2010.05.025 pmid: 20380420
	(b) Mai, S.; Luo, Y.; Huang, X.; Shu, Z.; Li, B.; Lan, Y.; Song, Q. Chem. Commun. 2018, 54, 10240. doi: 10.1039/C8CC05390A pmid: 20380420
	(c) Kochanowska-Karamyan, A. J.; Hamann, M. T. Chem. Rev. 2010, 110, 4489. doi: 10.1021/cr900211p pmid: 20380420
	(d) Li, N.; Li, C.; Han, R.; Wang, Y.; Yang, M.; Wang, H.; Tian, J. Front. Pharmacol. 2019, 10, 53. doi: 10.3389/fphar.2019.00053 pmid: 20380420
[14]	(a) Wei, W.; Ji, J.-X. Angew. Chem., Int. Ed. 2011, 50, 9097. doi: 10.1002/anie.201100219 pmid: 29136376
	(b) Zhou, Y.; Zhou, M.; Chen, M.; Su, J.; Du, J.; Song, Q. RSC Adv. 2015, 5, 103977. doi: 10.1039/C5RA23950H pmid: 29136376
	(c) Zhang, P.; Zhang, L.; Gao, Y.; Xu, J.; Fang, H.; Tang, G.; Zhao, Y. Chem. Commun. 2015, 51, 7839. doi: 10.1039/C5CC01904D pmid: 29136376
	(d) Zhou, Y.; Rao, C.; Mai, S.; Song, Q. J. Org. Chem. 2016, 81, 2027. doi: 10.1021/acs.joc.5b02887 pmid: 29136376
	(e) Zhou, P.; Hu, B.; Li, L.; Rao, K.; Yang, J.; Yu, F. J. Org. Chem. 2017, 82, 13268. doi: 10.1021/acs.joc.7b02391 pmid: 29136376
[15]	(a) Tang, Y.; Liu, J.; Yin, Q.; Huang, J.; Deng, S.; Jiang, J.; He, W.-M. J. Org. Chem. 2025, 90, 13165. doi: 10.1021/acs.joc.5c01775
	(b) Tang, Y.; Yang, Y.; Zhou, Q.; Duan, J.; Yang, B.; Du, C.; He, Y. Org. Biomol. Chem. 2023, 21, 5254. doi: 10.1039/D3OB00630A
	(c) Tang, Y.; Duan, J.; Yang, B.; He, Y.; Du, C.; Zhang, X. Org. Biomol. Chem. 2023, 21, 8152. doi: 10.1039/D3OB01289A
[16]	(a) Gui, Q.; Teng, F.; Li, Z.; Xiong, Z.; Jin, X.; Lin, Y.; Cao, Z.; He, W.-M. Chin. Chem. Lett. 2021, 32, 1907. doi: 10.1016/j.cclet.2021.01.021
	(b) Liu, C.; Zhang, Z.; Zhao, Z.; Jiang, J.; Yang, Z.; Wang, Z.-L.; He, W.-M. J. Org. Chem. 2025, 90, 11982. doi: 10.1021/acs.joc.5c01659
	(c) Jiang, S.-S.; Xiao, Y.-T.; Wu, Y.-C.; Luo, S.-Z.; Song, R.-J.; Li, J.-H. Org. Biomol. Chem. 2020, 18, 4843. doi: 10.1039/D0OB00877J

Entry	Oxidant	Solvent	Yield^b/%
1	Mn(OAc)₃•2H₂O	CH₃CN	40
2	Mn(OAc)₃•2H₂O	DMSO	43
3	Mn(OAc)₃•2H₂O	DCE	74
4	Mn(OAc)₃•2H₂O	DMF	45
5	Mn(OAc)₃•2H₂O	HOAc	44
6	Mn(OAc)₂	DCE	0
7	MnO₂	DCE	15
8	MnCl₂	DCE	0
9	AgNO₃	DCE	35
10	Fe(OTf)₃	DCE	Trace
11^c	Mn(OAc)₃•2H₂O	DCE	77
12^d	Mn(OAc)₃•2H₂O	DCE	75
13^e	Mn(OAc)₃•2H₂O	DCE	50
14^f	Mn(OAc)₃•2H₂O	DCE	40
15^g	Mn(OAc)₃•2H₂O	DCE	68

Entry	Oxidant	Solvent	Yield^b/%
1	Mn(OAc)₃•2H₂O	CH₃CN	40
2	Mn(OAc)₃•2H₂O	DMSO	43
3	Mn(OAc)₃•2H₂O	DCE	74
4	Mn(OAc)₃•2H₂O	DMF	45
5	Mn(OAc)₃•2H₂O	HOAc	44
6	Mn(OAc)₂	DCE	0
7	MnO₂	DCE	15
8	MnCl₂	DCE	0
9	AgNO₃	DCE	35
10	Fe(OTf)₃	DCE	Trace
11^c	Mn(OAc)₃•2H₂O	DCE	77
12^d	Mn(OAc)₃•2H₂O	DCE	75
13^e	Mn(OAc)₃•2H₂O	DCE	50
14^f	Mn(OAc)₃•2H₂O	DCE	40
15^g	Mn(OAc)₃•2H₂O	DCE	68

锰促进活化烯烃与亚磷酸酯串联磷酰化/环化反应合成γ-咔啉酮衍生物

Synthesis of γ-Carbolinone Derivatives via Manganese(III)-Promoted Tandem Phosphinoylation/Cyclization of Activated Alkenes with Phosphites

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 16

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Meng Liu, Taobo Liu, Meilan Han, Shuyang Wang, Zhipaicuo Gui, Guangli Xu, Hongping Han. Research Progress on Transition Metal-Catalyzed Carbosilylation of Alkenes [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 840-858.
[2]	Chunnian Xia, Kailin Chen, Nuoqi Jin, Xinhui Nan, Bingyang Wang, Xinyi Wu, Qiangsheng Sun, Wei Sun. Efficient Oxidation of Alcohols Using a Bioinspired Tetradentate Aminopyridine Manganese Catalyst with H₂O₂: Batch and Continuous Flow Studies [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 986-992.
[3]	Haifeng Yu, Yutong Sun, Shaohong Zhang, Ke Li, Xiaobo Zhao. Mn(OAc)₃ Promoted α-C—H Phosphonation of α-Oxo Ketene Dithioacetals with Dialkyl Phosphonates [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 925-933.
[4]	Wenjing Li, Siyu Shen, Lingling Liang, Xuejiao Zhang, Yanqing Miao, Jing You. Visible Light-Promoted Oxidative Cleavage of Alkene Using an Organic Photocatalyst [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 633-640.
[5]	Rundong Fan, Bingran Chen, Fuqi Li, Jinxiu Chen, Qiongjiao Yan, Wei Wang, Hui Zhou. Photosensitizer-Free Photoinduced Hydrodifluoroalkylation of α‑Trifluoromethyl Alkenes [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 641-652.
[6]	Weibao He, Mengyun He, Qiong Liao, Rongnan Yi. NaNO₂ Mediated Difunctionalizations of Alkenes for the Synthesis of β-Oximino Phosphorodithioates [J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 515-522.
[7]	Wen Xu, Meiming Luo, Xiaoming Zeng. Cr-Catalyzed Reductive Cross-Coupling of Trifluoromethyl Alkenes [J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3401-3411.
[8]	Tianbao Liu, Doudou Miao, Yanfen Peng, Min Zhang, Meifang Gui, Weilong Bi, Yawen Zong. Microwave-Assisted Synthesis of 2-Acylamino Naphthothiazole Derivatives [J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2612-2619.
[9]	Chao Wang, Hongping Chen, Mingzhong Mi, Aowen Li, Yan Qi, Yongjun Liu. Application of Manganese Catalysts in Coupling Reactions in Organic Synthesis [J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2326-2334.
[10]	Haichen Ma, Junqian Zhou, Jiali Wang, You Wang, Shaolin Zhu. Recent Advances in Ni-Catalyzed Migratory Cross-Coupling Reactions [J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 1871-1904.
[11]	Shixun Guo, Wei Wang, Yongqiang Zhang. Research of Triplet Energy Transfer Enabled Radical-Chain Hydroarylation of Alkenes [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1716-1728.
[12]	Junjie Liu, Hongping Zhao, Yuanyuan Hu, Hengxin Wang, Weiming Yuan. Photoinduced Nickel-Catalyzed Reductive Heck Reaction [J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1691-1697.
[13]	Enze Lin, Bijie Li. Recent Progress in Metal-Catalyzed Asymmetric Hydroarylation of Internal Alkenes Through C—H Cleavage [J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 546-558.
[14]	Ruhai Lin, Wei Mao, Donghuai Tu, Xingzong Dong, Hui Ma, Jian Lü. Synthesis of cis-Alkene with Electron-Withdrawing Groups via Photocatalytic Isomerization [J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4390-4397.
[15]	Zengfeng Li, Chengxi Li, Piao Zhang, Jinmeng Tang, Chifan Zhu, Guodong Hu, Meihua Shen, Hua-Dong Xu. Design and Synthesis of Peptide-Based Salen-Co(II) Complexes, and Studies on Their Catalytic Reactivity in Alkene Hydrohydrazination [J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4425-4432.