Silver/Ganphos-Catalyzed Enantioselective [3＋2] Cycloadditions of Azomethine Ylides: Access to the Spirocyclic Scaffolds

doi:10.6023/cjoc202502019

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (9): 3458-3468.DOI: 10.6023/cjoc202502019 Previous Articles Next Articles

ARTICLES

银/Ganphos催化甲亚胺叶立德的对映选择性[3＋2]环加成反应: 构筑螺旋环骨架

徐梦雅^a, 李一凡^a, 王越^b^,^*(), 韩瑞萍^a, 李二庆^a^,^*()

^a 郑州大学化学学院郑州 450001
^b 河南工业大学前沿交叉科学与技术学院河南省分子耦合技术与应用重点实验室郑州 450000

收稿日期:2025-02-18 修回日期:2025-04-08 发布日期:2025-05-06
基金资助:
国家自然科学基金(21702189); 科技研究发展计划联合基金(优势学科培育)(222301420042); 郑州大学资助项目

Silver/Ganphos-Catalyzed Enantioselective [3＋2] Cycloadditions of Azomethine Ylides: Access to the Spirocyclic Scaffolds

Mengya Xu^a, Yifan Li^a, Yue Wang^b^,^*(), Ruiping Han^a, Er-Qing Li^a^,^*()

^a College of Chemistry, Zhengzhou University, Zhengzhou 450001
^b Henan Linker Technology Key Laboratory, College of Advanced Interdisciplinary Science and Technology (CAIST), Henan University of Technology, Zhengzhou 450001

Received:2025-02-18 Revised:2025-04-08 Published:2025-05-06
Contact: *E-mail: wangyue@haut.edu.cn; lierqing@zzu.edu.cn
Supported by:
National Natural Science Foundation of China(21702189); Science and Technology Research and Development Plan Joint Fund (Cultivation of Superior Disciplines) Project(222301420042); Zhengzhou University

1. .pdf(6318KB)

Abstract

A Silver-catalyzed enantioselective [3＋2] cycloaddition of azomethine ylides with activated alkenes by using a P-stereogenic ligand Ganphos is reported. The method provides an efficient strategy for the effective synthesis of spirocyclic scaffolds containing a pyrroline motif. Notable features of this approach include good yields, remarkable enantioselectivity, as well as a broad substrate scope and significant step efficiency.

Key words: cycloaddition, silver catalysis, Ganphos, pyrroline

Cite this article

Mengya Xu, Yifan Li, Yue Wang, Ruiping Han, Er-Qing Li. Silver/Ganphos-Catalyzed Enantioselective [3＋2] Cycloadditions of Azomethine Ylides: Access to the Spirocyclic Scaffolds[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3458-3468.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

References 18

[1]	(a) Wang, J.; Cady, S. D.; Balannik, V.; Pinto, L. H.; DeGrado, W. F.; Hong, M. J. Am. Chem. Soc. 2009, 131, 8066. doi: 10.1021/ja900063s pmid: 25255204
	(b) Abad-Grillo, T.; McNaughton-Smith, G. Molecule 2024, 29, 4811. pmid: 25255204
	(c) Vitaku, E.; Smithand, D. T.; Njardarson, J. T. J. Med. Chem. 2014, 57, 10257. doi: 10.1021/jm501100b pmid: 25255204
[2]	Martyn, D. C.; Ramirez, A. P.; Beattie, M. J.; Cortese, J. F.; Patel, V.; Rush, M. A.; Woerpel, K. A.; Clardy, J. Bioorg. Med. Chem. Lett. 2008, 18, 6521. doi: 10.1016/j.bmcl.2008.10.083 pmid: 18993067
[3]	Reilly, S. W.; Puentes, L. N.; Wilson, K.; Hsieh, C.-J.; Weng, C.-C.; Makvandi, M.; Mach, R. H. J. Med. Chem. 2018, 61, 5367. doi: 10.1021/acs.jmedchem.8b00576 pmid: 29856625
[4]	Alen, J.; Schade, M.; Wagener, M.; Christian, F.; Nordhoff, S.; Merla, B.; Dunkern, T. R.; Bahrenberg, G.; Ratcliffe, P. J. Med. Chem. 2019, 62, 6391. doi: 10.1021/acs.jmedchem.9b00218 pmid: 31244106
[5]	Noble, S.; Sorkin, E. M. Drugs 1995, 49, 750. pmid: 7601014
[6]	Duvvuru, D.; Pinto, N.; Gomez, C.; Betzer, J.-F.; Retailleau, P.; Voituriez, A.; Marinetti, A. Adv. Synth. Catal. 2012, 354, 408.
[7]	Gan, Z.; Zhi, M.; Han, R.; Li, E.-Q.; Duan, Z.; Mathey, F. Org. Lett. 2019, 21, 2782.
[8]	Allway, P.; Grigg, R. Tetrahedron Lett. 1991, 32, 5817.
[9]	(a) Fang, X.; Wang, C.-J. Org. Biomol. Chem. 2018, 16, 2591. doi: 10.1039/C7OB02686B pmid: 11848917
	(b) Hashimoto, T.; Maruoka, K. Chem. Rev. 2015, 115, 5366. doi: 10.1021/cr5007182 pmid: 11848917
	(c) Adrioand, J.; Carretero, J. C. Chem. Commun. 2014, 50, 12434. pmid: 11848917
	(d) Narayan, R.; Potowski, M.; Jia, Z.-J.; Antonchick, A. P.; Waldmann, H. Acc. Chem. Res., 2014, 47, 1296. pmid: 11848917
	(e) Adrioand, J.; Carretero, J. C. Chem. Commun. 2011, 47, 6784. pmid: 11848917
	(f) Stanley, L. M.; Sibi, M. P. Chem. Rev. 2008, 108, 2887. doi: 10.1021/cr078371m pmid: 11848917
	(g) Pandey, G.; Banerjee, P.; Gadre, S. R. Chem. Rev. 2006, 106, 4484. pmid: 11848917
	(h) Gothelf, K. V.; Jørgensen, K. A. Chem. Rev. 1998, 98, 863. pmid: 11848917
[10]	(a) Liu, H.-C.; Wei, L.; Huang, R.; Tao, H.-Y.; Cong, H.; Wang, C.-J. Org. Lett. 2018, 20, 3482. doi: 10.1021/acs.orglett.8b01254 pmid: 29846076
	(b) Yao, L.; Zhu, Q.; Wei, L.; Wang, Z.-F.; Wang, C.-J. Angew. Chem., Int. Ed. 2016, 55, 5829. pmid: 29846076
[11]	Cabrera, S.; Arrayas, R. G.; Carretero, J. C. J. Am. Chem. Soc. 2005, 127, 16394. pmid: 16305216
[12]	Su, X.; Zhou, W.; Li, Y.; Zhang, J. Angew. Chem., Int. Ed. 2015, 54, 6874.
[13]	Oura, I.; Shimizu, K.; Ogata, K.; Fukuzawa, S. Org. Lett. 2010, 12, 1752.
[14]	Bai, X.-F.; Song, T.; Xu, Z.; Xia, C.-G; Huang, W.-S.; Xu, L.-W. Angew. Chem., Int. Ed. 2015, 54, 5255.
[15]	(a) Meng, Q.; Meng, Y.; Liu, Q.; Yu, B.; Li, Z.-J.; Li, E.-Q.; Zhang, J. Adv. Sci. 2024, 11, 2402170. pmid: 35919424
	(b) Wang, Y.; Li, E.-Q.; Duan, Z. Chem. Sci. 2022, 13, 8131. doi: 10.1039/d2sc02771b pmid: 35919424
	(c) Meng, Y.; Wang, Q.; Yao, X.; Wei, D.; Liu, Y.-G.; Li, E.-Q.; Duan, Z. Org. Lett. 2022, 24, 9205. pmid: 35919424
	(d) Jia, S.; Ma, M.; Li, E.-Q.; Duan, Z.; Mathey, F. Org. Lett. 2021, 23, 3337. pmid: 35919424
	(e) Cui, H.; Li, K.; Wang, Y.; Song, M.; Wang, C.; Wei, D.; Li, E.-Q.; Duan, Z.; Mathey, F. Org. Biomol. Chem. 2020, 18, 3740. pmid: 35919424
[16]	(a) Wang, R.; Wang, S.-Y.; Ji, S.-J. Org. Biomol. Chem. 2014, 12, 1735.
	(b) Duan, D.-H.; Wei, Y.-F.; Li, T.-Y.; Gong, Q.; Shen, M.; Zhu, F.; Liu, S.-L. J. Org. Chem. 2024, 89, 11959.
	(c) Hu, Z.-P.; Lou, C.-L.; Wang, J.-J.; Chen, C.-X.; Yan, M. J. Org. Chem. 2011, 76, 3797.
[17]	Ye, D.-N.; Peng, X.-J.; Bdiri, B.; Li, C.; Zhou, Z.-M. Tetrahedron: Asymmetry 2017, 28, 1044.
[18]	Zhi, M.; Gan, Z.; Ma, R.; Cui, H.; Li, E.-Q.; Duan, Z.; Mathey, F. Org. Lett. 2019, 21, 3210.

Entry	L	Solvent	Yield^b/%	ee^c/%
1	L1'	THF	95	51
2	L1'	DCM	74	55
3	L1'	CH₃CN	92	72
4	L1'	Toluene	70	44
5	L1	CH₃CN	99	-39
6	L2	CH₃CN	96	-29
7	L2'	CH₃CN	>99	60
8	L3	CH₃CN	96	-7
9	L3'	CH₃CN	89	50
10	L4	CH₃CN	91	-27
11	L4'	CH₃CN	95	61
12	L5'	CH₃CN	>99	33
13	L6'	CH₃CN	>99	61
14	S1	CH₃CN	96	-6
15	S2	CH₃CN	96	30
16^d	L1'	CH₃CN	>99	73
17^d^,^e	L1'	CH₃CN	94	75
18^d^,^e^,^f	L1'	CH₃CN	>99	71
19^d^,^e^,^g	L1'	CH₃CN	>99	83
20^d^,^e^,^h	L1'	CH₃CN	>99	84
21^d^,^e^,^g^,ⁱ	L1'	CH₃CN	>99	97

Entry	L	Solvent	Yield^b/%	ee^c/%
1	L1'	THF	95	51
2	L1'	DCM	74	55
3	L1'	CH₃CN	92	72
4	L1'	Toluene	70	44
5	L1	CH₃CN	99	-39
6	L2	CH₃CN	96	-29
7	L2'	CH₃CN	>99	60
8	L3	CH₃CN	96	-7
9	L3'	CH₃CN	89	50
10	L4	CH₃CN	91	-27
11	L4'	CH₃CN	95	61
12	L5'	CH₃CN	>99	33
13	L6'	CH₃CN	>99	61
14	S1	CH₃CN	96	-6
15	S2	CH₃CN	96	30
16^d	L1'	CH₃CN	>99	73
17^d^,^e	L1'	CH₃CN	94	75
18^d^,^e^,^f	L1'	CH₃CN	>99	71
19^d^,^e^,^g	L1'	CH₃CN	>99	83
20^d^,^e^,^h	L1'	CH₃CN	>99	84
21^d^,^e^,^g^,ⁱ	L1'	CH₃CN	>99	97

银/Ganphos催化甲亚胺叶立德的对映选择性[3＋2]环加成反应: 构筑螺旋环骨架

Silver/Ganphos-Catalyzed Enantioselective [3＋2] Cycloadditions of Azomethine Ylides: Access to the Spirocyclic Scaffolds

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 18

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Zunqi Liu, Jahangir Khan, Muhammad Akram, Yasir Mumtaz. Recent Advances in the Synthesis and Applications of Isothiocyanates [J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2350-2366.
[2]	Xiaofeng Zhang, Aggeliki Roumana, Haikang Mao, Jing Xu. Synthesis of the AB Ring System of Daphniphyllum Alkaloid Daphniglaucin C [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 925-932.
[3]	Yanben Wang, Zuming Lin, Sha-Hua Huang, Lili Zhu, Ran Hong. Enantiodivergent Synthesis of (+)- and (–)-Crispine A [J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 1021-1029.
[4]	Yefei Zhang, Yong Tang, You-Yun Zhou. Progress in [4＋1] Cycloadditions of Conjugated Dienes [J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 1-21.
[5]	Xiaomei Wang, Yan Liu, Shiwu Li, Zhifei Zhao. N-Heterocyclic Carbene-Catalyzed [4＋2] Cycloaddition of Salicylaldehydes with Pyrazole-4,5-diones for the Synthesis of Spiroketal-Pyrazolones [J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 267-275.
[6]	Xiaonan Mu, Minhui Guan, Yulong Niu, Hao Chen, Chuanying Li, Lei Wang. Synthesis of Difluorocyclopropanes via a Photoinduced [1＋2] Cycloaddition of Diazo Esters with gem-Difluoroalkenes [J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 256-266.
[7]	Ying Fan, Danfeng Huang, Hu Ma, Zuyu Bai, Ke-Hu Wang, Junjiao Wang, Yulai Hu. Synthesis of Difluoromethyl Substituted 1,2,4-Triazoline Compounds [J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2820-2831.
[8]	Jia-Xi Jiang, Quan-Zhong Liu. Non-Metallic Carbene Pathway Transformations of Vinyl Diazo Compounds [J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2640-2657.
[9]	Yu Zeng, Zhonghao Li, Siwei Deng, Zujia Chen, Biyu Chen, Shiwei Yu, Qing Shen, Zhaoyang Wang. Research Progress on Preparation and Application of Cyanoethylenes [J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2722-2731.
[10]	Xixian Cao, Jun You, Qiye Liu, Bo Liu, Yanchao Yu, Wenju Wu. (4S,4'S)-2,2'-(4,6-Dibenzofurandiyl)bis[4,5-dihydro-4-phenyloxazole]-Ni(II) Complexes Catalyzed Highly Enantioselective Nitrile Imine Cycloaddition Reactions [J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2315-2332.
[11]	Shulin Zhang, Zhou Zhang, Meng Sun. Ag(I)-Catalyzed Addition of Cyclopropenones and Alcohols via C—C Bond Cleavage [J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2233-2240.
[12]	Yongwei Cui, Chunmiao Liang, Haitao Zhu, Chengping Shen, Feiyang Ren, Menghan Sun, Yuan Zhao, Wenjing Wang, Dongmei Wang, Nini Zhou. cis-Selective [5＋2]-Cycloaddition Reactions of Cyclic Morita-Baylis- Hillman Alcohols and Its Analogues with Arylethylenes Catalyzed by Ag(I) [J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1535-1548.
[13]	Yan Liu, Xiaomei Wang, Lin He, Shiwu Li, Zhifei Zhao. N-Heterocyclic Carbene (NHC)-Catalyzed [3+2] Cycloaddition to Highly Diastereoselective Synthesis of Spirooxindole Dihydrofuran Fused Pyrazolone Compounds [J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1301-1310.
[14]	Chen-Long Li, Zhi-Xiang Yu. Progress in Transition-Metal-Catalyzed Carbonylative Cycloadditions Using Carbon Monoxide [J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1045-1068.
[15]	Yingzhe Zhao, Zixuan Zhang, Jianling Zhang, Renjie Zhang, Meiling Li, Yunan Teng, Haoxiang Wang. Synthesis of Cerium Doped Zirconium-Based Metal-Organic Framework Nanoparticles and Their Photocatalytic Performance for Carbon Dioxide Cycloaddition [J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3169-3177.