Phosphine-Catalyzed [2＋3] Annulation of Aurone-Derived Azadienes with Amino Crotonates

doi:10.6023/cjoc202501015

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (6): 2139-2148.DOI: 10.6023/cjoc202501015 Previous Articles Next Articles

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有机膦催化下橙酮衍生的氮杂二烯与氨基巴豆酸酯的[2＋3]环加成反应

陈刚^†, 陈东^†, 聂广杰, 李林轩, 姚辉, 王能中^*(), 黄年玉^*()

三峡大学生物与制药学院天然产物研究与利用湖北省重点实验室湖北宜昌 443002

收稿日期:2025-01-15 修回日期:2025-03-03 发布日期:2025-03-24
通讯作者: 王能中, 黄年玉
作者简介:
^†共同第一作者.
基金资助:
国家自然科学基金(22207063); 高等学校学科创新引智计划（111计划）(D20015); 宜昌市自然科学研究项目(A23-2-002); 天然产物研究与利用湖北省重点实验室(三峡大学)开放基金(2024NPRD03); 天然产物研究与利用湖北省重点实验室(三峡大学)开放基金(2024NPRD04); 天然产物研究与利用湖北省重点实验室(三峡大学)开放基金(2024NPRD05)

Phosphine-Catalyzed [2＋3] Annulation of Aurone-Derived Azadienes with Amino Crotonates

Gang Chen^†, Dong Chen^†, Guangjie Nie, Linxuan Li, Hui Yao, Nengzhong Wang^*(), Nianyu Huang^*()

Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei 443002

Received:2025-01-15 Revised:2025-03-03 Published:2025-03-24
Contact: Nengzhong Wang, Nianyu Huang
About author:
^†The authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22207063); Programme of Introducing Talents of Discipline to Universities (111 Project)(D20015); Natural Science Research Project of Yichang City(A23-2-002); Opening Funding of Hubei Key Laboratory of Natural Products Research and Development, China Three Gorges University(2024NPRD03); Opening Funding of Hubei Key Laboratory of Natural Products Research and Development, China Three Gorges University(2024NPRD04); Opening Funding of Hubei Key Laboratory of Natural Products Research and Development, China Three Gorges University(2024NPRD05)

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Abstract

This paper reports a phosphine-catalyzed [2＋3] annulation reaction between aurone-derived azadienes and amino crotonates, yielding a series of spiro[benzofuran-tetrahydropyrrole] compounds bearing three consective sterecenters in high yields with moderate to excellent diastereoselectivities. The structures of the desired products were determined by a combination of NMR sprctroscopy, high-resolution mass spectrometry (HRMS) and X-ray single crystal diffraction analysis. This method has the advantages of simple operation, broad substrate scope and 100% atom economy, which provides a new idea for the effecient construction of spiro[benzofuran-tetrahydropyrrole] compounds.

Key words: phosphine catalysis, [2＋3] annulation, aurone-derived azadienes, amino crotonates, spirocyclic compounds

Cite this article

Gang Chen, Dong Chen, Guangjie Nie, Linxuan Li, Hui Yao, Nengzhong Wang, Nianyu Huang. Phosphine-Catalyzed [2＋3] Annulation of Aurone-Derived Azadienes with Amino Crotonates[J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2139-2148.

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Entry	Catalyst	Solvent	t/^oC	n(1a)∶n(2a)	Yield^b/%	d.r.^c
1	PBu₃	DCM	50	1.5∶1.0	73	12∶1
2	PPhEt₂	DCM	50	1.5∶1.0	70	10∶1
3	PPh₂Et	DCM	50	1.5∶1.0	57	7∶1
4	PPh₃	DCM	50	1.5∶1.0	8	>20∶1
5	P(2-MeC₆H₄)₃	DCM	50	1.5∶1.0	N.R.	—
6	P(2-MeOC₆H₄)₃	DCM	50	1.5∶1.0	81	12∶1
7	P(2-FC₆H₄)₃	DCM	50	1.5∶1.0	N.R.	—
8	P(4-MeOC₆H₄)₃	DCM	50	1.5∶1.0	38	8∶1
9	P(4-BrC₆H₄)₃	DCM	50	1.5∶1.0	N.R.	—
10	P(2,6-MeOC₆H₃)₃	DCM	50	1.5∶1.0	N.R.	—
11	P(2-MeOC₆H₄)₃	CHCl₃	50	1.5∶1.0	68	8∶1
12	P(2-MeOC₆H₄)₃	MeCN	50	1.5∶1.0	14	3∶1
13	P(2-MeOC₆H₄)₃	DMF	50	1.5∶1.0	32	6∶1
14	P(2-MeOC₆H₄)₃	Toluene	50	1.5∶1.0	N.R.	—
15	P(2-MeOC₆H₄)₃	THF	50	1.5∶1.0	N.R.	—
16	P(2-MeOC₆H₄)₃	EtOAc	50	1.5∶1.0	N.R.	—
17	P(2-MeOC₆H₄)₃	DCM	30	1.5∶1.0	N.R.	—
18	P(2-MeOC₆H₄)₃	DCM	40	1.5∶1.0	57	12∶1
19	P(2-MeOC₆H₄)₃	DCM	50	1.0∶1.0	66	12∶1
20	P(2-MeOC₆H₄)₃	DCM	50	2.0∶1.0	42	12∶1

Entry	Catalyst	Solvent	t/^oC	n(1a)∶n(2a)	Yield^b/%	d.r.^c
1	PBu₃	DCM	50	1.5∶1.0	73	12∶1
2	PPhEt₂	DCM	50	1.5∶1.0	70	10∶1
3	PPh₂Et	DCM	50	1.5∶1.0	57	7∶1
4	PPh₃	DCM	50	1.5∶1.0	8	>20∶1
5	P(2-MeC₆H₄)₃	DCM	50	1.5∶1.0	N.R.	—
6	P(2-MeOC₆H₄)₃	DCM	50	1.5∶1.0	81	12∶1
7	P(2-FC₆H₄)₃	DCM	50	1.5∶1.0	N.R.	—
8	P(4-MeOC₆H₄)₃	DCM	50	1.5∶1.0	38	8∶1
9	P(4-BrC₆H₄)₃	DCM	50	1.5∶1.0	N.R.	—
10	P(2,6-MeOC₆H₃)₃	DCM	50	1.5∶1.0	N.R.	—
11	P(2-MeOC₆H₄)₃	CHCl₃	50	1.5∶1.0	68	8∶1
12	P(2-MeOC₆H₄)₃	MeCN	50	1.5∶1.0	14	3∶1
13	P(2-MeOC₆H₄)₃	DMF	50	1.5∶1.0	32	6∶1
14	P(2-MeOC₆H₄)₃	Toluene	50	1.5∶1.0	N.R.	—
15	P(2-MeOC₆H₄)₃	THF	50	1.5∶1.0	N.R.	—
16	P(2-MeOC₆H₄)₃	EtOAc	50	1.5∶1.0	N.R.	—
17	P(2-MeOC₆H₄)₃	DCM	30	1.5∶1.0	N.R.	—
18	P(2-MeOC₆H₄)₃	DCM	40	1.5∶1.0	57	12∶1
19	P(2-MeOC₆H₄)₃	DCM	50	1.0∶1.0	66	12∶1
20	P(2-MeOC₆H₄)₃	DCM	50	2.0∶1.0	42	12∶1

有机膦催化下橙酮衍生的氮杂二烯与氨基巴豆酸酯的[2＋3]环加成反应

Phosphine-Catalyzed [2＋3] Annulation of Aurone-Derived Azadienes with Amino Crotonates

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