Efficient Construction of the Core Pentacyclic Skeleton of Communesin Alkaloids

doi:10.6023/cjoc202408006

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (3): 1003-1008.DOI: 10.6023/cjoc202408006 Previous Articles Next Articles

ARTICLES

Communesin生物碱核心五环骨架的高效合成

杨之同^a, 宋恒谦^a, 雷盼^a, 闫嘉航^a^,^*(), 谢卫青^a^,^b^,^*()

a 西北农林科技大学化学与药学院陕西杨凌 712100
b 陕西省植物源农药研究与开发重点实验室陕西杨凌 712100

收稿日期:2024-08-06 修回日期:2024-09-09 发布日期:2024-10-29
基金资助:
国家自然科学基金(22301245); 国家自然科学基金(22371231)

Efficient Construction of the Core Pentacyclic Skeleton of Communesin Alkaloids

Zhitong Yang^a, Hengqian Song^a, Pan Lei^a, Jiahang Yan^a(), Weiqing Xie^a^,^b()

a College of Chemistry & Pharmacy, Northwest A&F University, Yangling, Shaanxi 712100
b Key Laboratory for Botanical Pesticide R&D of Shaanxi Province, Yangling, Shaanxi 712100

Received:2024-08-06 Revised:2024-09-09 Published:2024-10-29
Contact: * E-mail: yanjiahang1015@163.com; xiewq@nwafu.edu.cn
Supported by:
National Natural Science Foundation of China(22301245); National Natural Science Foundation of China(22371231)

1. .pdf(2042KB)

Abstract

Communesin alkaloids are a family of complex dimeric cyclotryptamine alkaloids isolated from the marine fungi of the genus penicillium. These indole alkaloids contain a unique caged heptacyclic skeleton along with five stereogenic centers at least, two of which are the contiguous quaternary carbon centers (CQCCs), thus presenting remarkable synthetic challenges. Herein, an expedient construction core pentacyclic ring system of communesins is developed. The key steps include a catalytic asymmetric conjugated addition promoted by Ni(II)/chiral N,O-chiral dioxide for establishing the CQCCs and a deprotection/ring-opening reaction/cyclization cascade for setting up the pentacyclic skeleton.

Key words: communesin, contiguous quaternary carbon, asymmetric catalysis, conjugated addition, cascade cyclization

Cite this article

Zhitong Yang, Hengqian Song, Pan Lei, Jiahang Yan, Weiqing Xie. Efficient Construction of the Core Pentacyclic Skeleton of Communesin Alkaloids[J]. Chinese Journal of Organic Chemistry, 2025, 45(3): 1003-1008.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 6

References 15

[1]	Numata, A.; Takahashi, C.; Ito, Y.; Takada, T.; Kawai, K.; Usami, Y.; Matsumura, E.; Imachi, M.; Ito, T.; Hasegawa, T. Tetrahedron Lett. 1993, 34, 2355.
[2]	Dalsgaard, P. W.; Blunt, J. W.; Munro, M. H. G.; Frisvad, J. C.; Christophersen, C. J. Nat. Prod. 2005, 68, 258.
[3]	Jadulco, R.; Edrada, R. A.; Ebel, R.; Berg, A.; Schaumann, K.; Wray, V.; Steube, K.; Proksch, P. J. Nat. Prod. 2004, 67, 78.
[4]	Hayashi, H.; Matsumoto, H.; Akiyama, K. Biosci., Biotechnol., Biochem. 2004, 68, 753.
[5]	Yang, J.; Wu, H.; Shen, L.; Qin, Y. J. Am. Chem. Soc. 2007, 129, 13794.
[6]	(a) Zuo, Z. W.; Xie, W. Q.; Ma, D. W. J. Am. Chem. Soc. 2010, 132, 13226.
	(b) Zuo, Z. W.; Ma, D. W. Angew. Chem., Int. Ed. 2011, 50, 12008.
[7]	(a) Liu, P.; Seo, J. H.; Weinreb, S. M. Angew. Chem., Int. Ed. 2010, 49, 2000.
	(b) Seo, J. H.; Liu, P.; Weinreb, S. M. J. Org. Chem. 2010, 75, 2667.
[8]	Belmar, J.; Funk, R. L. J. Am. Chem. Soc. 2012, 134, 16941.
[9]	(a) Lathrop, S. P.; Pompeo, M.; Chang, W. T.; Movassaghi, M. J. Am. Chem. Soc. 2016, 138, 7763.
	(b) Pompeo, M.; Cheah, J. H.; Movassaghi, M. J. Am. Chem. Soc. 2019, 141, 14411.
[10]	Park, J.; Jean, A.; Chen David, Y. K. Angew. Chem., Int. Ed. 2017, 56, 14237.
[11]	Liang, X.; Zhang, T. Y.; Zeng, X. Y.; Zheng, Y.; Wei, K.; Yang, Y. R. J. Am. Chem. Soc. 2017, 139, 3364.
[12]	For review on chiral N,N'-dioxide ligand: (a) Liu, X. H.; Lin, L. L.; Feng X. M. Org. Chem. Front. 2014, 1, 298.
	(b) Liu, X. H.; Zheng, H. F.; Xia, Y.; Lin, L. L.; Feng, X. M. Acc. Chem. Res. 2017, 50, 2621.
	For construction of contiguous quaternary carbon centers: (c) Zhang, H. L.; Hong, L.; Kang, H.; Wang, R. J. Am. Chem. Soc. 2013, 135, 14098.
	(d) Zheng, J. F.; Lin, L. L.; Dai, L.; Tang, Q.; Liu, X. H.; Feng, X. M. Angew. Chem., Int. Ed. 2017, 56, 13107.
	(e) Xu, J.; Zhong, Z. W.; Jiang, M. Y.; Zhou, Y. Q.; Liu, X. H.; Feng, X. M. CCS Chem. 2020, 2, 1894.
	(f) Xu, J.; Li, R. Z.; Xu, N.; Liu, X. H.; Wang, F.; Feng, X. M. Org. Lett. 2021, 23, 1856.
[13]	Xie, W. Q.; Jiang, G. D.; Liu, H.; Hu, J. D.; Pan, X. X.; Zhang, H.; Wan, X. L.; Lai, Y. S.; Ma, D. W. Angew. Chem., Int. Ed. 2013, 52, 12924.
[14]	(a) Wei, H. B.; Chen, G. Z.; Zou, H. H.; Zhou, Z. Q.; Lei, P.; Yan, J. H.; Xie, W. Q. Org. Chem. Front. 2021, 8, 3255.
	(b) Huo, J. Y.; Li, X. H.; Chen, Q. H.; Gao, P. P.; Hou, Y.; Lei, P.; Zou, H. H.; Yan, J. H.; Wan, X. L.; Xie, W. Q. ACS Catal. 2023, 13, 15007.
[15]	Xu, Y. Z.; Lei, P.; Fei, Y. A.; Hou, Y.; Chen, G. Z.; Zhou, Z. Q.; Zou, H. H.; Wei, H. B.; Xie, W. Q. Tetrahedron Lett. 2023, 114, 154261.

Entry	Ni (II)	Ligand	Base	Yield^b/%	ee^c/%	dr^d
1	NiCl₂	L1	DIPEA	35	35	5∶1
2	Ni(ClO₄)₂•6H₂O	L1	DIPEA	53	71	8∶1
3	Ni(BF₄)₂•6H₂O	L1	DIPEA	43	73	>20∶1
4	Ni(BF₄)₂•6H₂O	L2	DIPEA	45	58	>20∶1
5	Ni(BF₄)₂•6H₂O	L3	DIPEA	40	93	>20∶1
6	Ni(BF₄)₂•6H₂O	L4	DIPEA	40	95	>20∶1
7	Ni(BF₄)₂•6H₂O	L4	Et₃N	58	84	>20∶1
8	Ni(BF₄)₂•6H₂O	L4	KHCO₃	35	95	>20∶1
9	Ni(BF₄)₂•6H₂O	L4	2,6-Lutidine	23	91	>20∶1

Entry	Ni (II)	Ligand	Base	Yield^b/%	ee^c/%	dr^d
1	NiCl₂	L1	DIPEA	35	35	5∶1
2	Ni(ClO₄)₂•6H₂O	L1	DIPEA	53	71	8∶1
3	Ni(BF₄)₂•6H₂O	L1	DIPEA	43	73	>20∶1
4	Ni(BF₄)₂•6H₂O	L2	DIPEA	45	58	>20∶1
5	Ni(BF₄)₂•6H₂O	L3	DIPEA	40	93	>20∶1
6	Ni(BF₄)₂•6H₂O	L4	DIPEA	40	95	>20∶1
7	Ni(BF₄)₂•6H₂O	L4	Et₃N	58	84	>20∶1
8	Ni(BF₄)₂•6H₂O	L4	KHCO₃	35	95	>20∶1
9	Ni(BF₄)₂•6H₂O	L4	2,6-Lutidine	23	91	>20∶1

Communesin生物碱核心五环骨架的高效合成

Efficient Construction of the Core Pentacyclic Skeleton of Communesin Alkaloids

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 6

References 15

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	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.
[2]	Yu Zou, Weicong Guo, Jun Wang. Application of Planar Chiral Cyclopentadienyl Rhodium Catalysts without Chiral Substituents in Asymmetric C—H Activation [J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 466-476.
[3]	Jiasheng Wang, Zeshu Wang, Weimin He, Longwu Ye. Research Progress on the Hydroamination of o-Alkynylanilines for the Synthesis of Axially Chiral Indoles [J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1786-1792.
[4]	Chenguang Liu. Progress in Asymmetric Hydrogenation of Aromatic N-Heterocyclic Compounds [J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1403-1422.
[5]	Fan Yang, Ting Fang, Guichun Yang, Meng Gao. Electrochemical Cascade Cyclization Reactions of Nitrosobenzenes in Construction of Quinolines and Pyrroles [J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 1021-1030.
[6]	Chun Gao, Xin Liu, Minghui Wang, Shuxian Liu, Tingting Zhu, Yikang Zhang, Erjun Hao, Qiliang Yang. Advances in Asymmetric Electrochemical Synthesis [J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 673-727.
[7]	Shuang Yang, Xinqiang Fang. Kinetic Resolutions Enabled by N-Heterocyclic Carbene Catalysis: An Update [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 448-480.
[8]	Wanting Chen, Xiongwei Zhong, Jiale Xing, Changshu Wu, Yang Gao. Progress in Asymmetric Catalytic Synthesis of C—N Axis Chiral Compounds [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 349-377.
[9]	Tingjia Sun, Guoyin Sun, Wei Sun, Xuesong Peng, Juan Liao, Yong You, Weicheng Yuan. Advances in Catalytic Asymmetric Hydrogen-Phosphine/Phosphorus Functionalization of Unsaturated Carbon-Carbon Bonds [J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3647-3677.
[10]	Jiao Long, Baixue Liu, Shuangshuang Zhang, Yuanyuan Zhu, Shuangxi Gu. Recent Advances in Nickel-Catalyzed Asymmetric Hydrofunctionalization of 1,3-Dienes [J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3309-3320.
[11]	Quanbin Jiang. Progress in Synthesis of Axially Chiral Compounds through aza-Vinylidene o-Quinone Methide Intermediates [J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 159-172.
[12]	Chun-Xia Cheng, Lu-Ping Wu, Feng Sha, Xin-Yan Wu. Enantioselective Vinylogous Allylic Alkylation of Coumarins with Morita-Baylis-Hillman Carbonates Catalyzed by Chiral Phosphine-Amide [J]. Chinese Journal of Organic Chemistry, 2023, 43(9): 3188-3195.
[13]	Cheng Luo, Yanli Yin, Zhiyong Jiang. Recent Advances in Asymmetric Synthesis of P-Chiral Phosphine Oxides [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 1963-1976.
[14]	Jingpeng Li, Shuntao Huang, Qi Yang, Weiqiang Li, Teng Liu, Chao Huang. A Practical Synthesis of (Z)-N-Vinyl Substituted N,O-Acetals under Continuous Flow Technology [J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1550-1558.
[15]	Siqiang Fang, Zanjiao Liu, Tianli Wang. Recent Advances of the Atherton-Todd Reaction [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1069-1083.