Study on Gold Self-Relay Catalytic Annulation/Nucleophilic Substitution of 1,3-Enyne Acetates with Cyclic Ether Acetals

doi:10.6023/cjoc202408027

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (6): 2199-2207.DOI: 10.6023/cjoc202408027 Previous Articles Next Articles

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金自接力催化1,3-烯炔醋酸酯与环醚缩醛的环化/亲核取代反应研究

张丛玉^†, 陈晓琦^†, 孟凡涛, 王海营^*(), 郝文娟, 姜波^*()

江苏师范大学化学与材料科学学院江苏徐州 221116

收稿日期:2024-08-22 修回日期:2024-10-16 发布日期:2024-11-27
通讯作者: 王海营, 姜波
作者简介:
^†共同第一作者.
基金资助:
国家自然科学基金(22271123); 国家级大学生创新创业训练计划(202410320046Z)

Study on Gold Self-Relay Catalytic Annulation/Nucleophilic Substitution of 1,3-Enyne Acetates with Cyclic Ether Acetals

Congyu Zhang^†, Xiaoqi Chen^†, Fantao Meng, Haiying Wang^*(), Wen-Juan Hao, Bo Jiang^*()

School of Chemistry & Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116

Received:2024-08-22 Revised:2024-10-16 Published:2024-11-27
Contact: Haiying Wang, Bo Jiang
About author:
^†The authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22271123); National College Students’ Innovation and Entrepreneurship Training Program(202410320046Z)

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Abstract

A new gold self-relay catalytic annulation/nucleophilic substitution cascade of 1,3-enyne acetates with cyclic ether acetals is reported, enabling highly diastereoselective access to cyclic etherified cyclopentenones with cyclic quaternary centers in moderate to good yields and >19∶1 dr. This catalysis enables the direct construction of two types of carboncyclic skeletons by adjusting the olefin types of 1,3-enyne acetates. When 1,3-enyne acetates bearing a cyclic alkene unit were used, 5~6 fused bicarbocyclic products were diastereoselectively synthesized, whereas the reaction of acyclic 1,3-enyne acetates resulted in five-memebered carbocyclic framework. Notably, cyclic ether acetals are commonly used as protecting groups in traditional multistep organic syntheses, and in this reaction, such reagents serve as electrophilic cyclic ether precursors, achieving new uses for old reagents. The current method demonstrates good functional group compatibility, a broad substrate scope and high diastereoselectivity, providing a new synthetic strategy toward functionalized cyclopentenones.

Key words: gold self-relay catalysis, Nazarov cyclization, nucleophilic substitution, 1,3-enyne acetates, cyclic ether acetals

Cite this article

Congyu Zhang, Xiaoqi Chen, Fantao Meng, Haiying Wang, Wen-Juan Hao, Bo Jiang. Study on Gold Self-Relay Catalytic Annulation/Nucleophilic Substitution of 1,3-Enyne Acetates with Cyclic Ether Acetals[J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2199-2207.

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Entry	n(1a)∶ n(2a)	[Au]	Solvent	Yield/ %
1	1∶1	JohnPhosAu(MeCN)SbF₆	DCM	33
2	1∶1.5	JohnPhosAu(MeCN)SbF₆	DCM	58
3	1∶2	JohnPhosAu(MeCN)SbF₆	DCM	52
4	1∶1.5	JohnPhosAu(MeCN)SbF₆	Toluene	71
5	1∶1.5	JohnPhosAu(MeCN)SbF₆	CH₃CN	69
6	1∶1.5	JohnPhosAu(MeCN)SbF₆	1,4-Dioxane	Trace
7	1∶1.5	JohnPhosAu(MeCN)SbF₆	THF	Trace
8	1∶1.5	PPh₃AuCl	Toluene	40
9	1∶1.5	AuCl	Toluene	16
10	1∶1.5	AuCl₃	Toluene	N.D.
11	1∶1.5	IPrAuNTf₂	Toluene	N.R.
12	1∶1.5	—	Toluene	N.R.

Entry	n(1a)∶ n(2a)	[Au]	Solvent	Yield/ %
1	1∶1	JohnPhosAu(MeCN)SbF₆	DCM	33
2	1∶1.5	JohnPhosAu(MeCN)SbF₆	DCM	58
3	1∶2	JohnPhosAu(MeCN)SbF₆	DCM	52
4	1∶1.5	JohnPhosAu(MeCN)SbF₆	Toluene	71
5	1∶1.5	JohnPhosAu(MeCN)SbF₆	CH₃CN	69
6	1∶1.5	JohnPhosAu(MeCN)SbF₆	1,4-Dioxane	Trace
7	1∶1.5	JohnPhosAu(MeCN)SbF₆	THF	Trace
8	1∶1.5	PPh₃AuCl	Toluene	40
9	1∶1.5	AuCl	Toluene	16
10	1∶1.5	AuCl₃	Toluene	N.D.
11	1∶1.5	IPrAuNTf₂	Toluene	N.R.
12	1∶1.5	—	Toluene	N.R.

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金自接力催化1,3-烯炔醋酸酯与环醚缩醛的环化/亲核取代反应研究

Study on Gold Self-Relay Catalytic Annulation/Nucleophilic Substitution of 1,3-Enyne Acetates with Cyclic Ether Acetals

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