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

doi:10.6023/cjoc202408027

有机化学 ›› 2025, Vol. 45 ›› Issue (6): 2199-2207.DOI: 10.6023/cjoc202408027 上一篇下一篇

研究论文

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)

文章分享

1. 2199辅助材料.pdf(4561KB)

摘要/Abstract

报道了一种新型金自接力催化1,3-烯炔醋酸酯与环醚缩醛参与的增环/亲核取代反应, 高非对映选择性地合成了具有环季碳中心的环醚化环戊烯酮衍生物, 收率中等至良好, dr值>19∶1. 该催化反应通过调整1,3-烯炔醋酸酯的烯烃类型实现了两类碳环骨架构建. 当使用具有环烯烃的1,3-烯炔醋酸酯时, 高非对映选择性地合成了5~6稠合双碳环产物, 而使用非环状1,3-烯炔醋酸酯时, 则形成五元碳环骨架. 值得一提的是, 环醚缩醛在传统多步有机合成中常用作保护基团, 而在此反应中, 该试剂用作亲电性的环醚前体, 实现旧试剂新用途. 目前方法展现出良好官能团相容性、广泛底物范围和高非对映选择性等优点, 为官能化环戊烯酮衍生物的合成提供一类新合成策略.

关键词: 金自接力催化, Nazarov环化, 亲核取代反应, 1,3-烯炔醋酸酯, 环醚缩醛

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

引用此文

张丛玉, 陈晓琦, 孟凡涛, 王海营, 郝文娟, 姜波. 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[J]. 有机化学, 2025, 45(6): 2199-2207.

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.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

参考文献 14

[1]	(a) Ye, L.-W.; Zhu, X.-Q.; Sahani, R. L.; Xu, Y.; Qian, P.-C.; Liu, R.-S. Chem. Rev. 2021, 121, 9039.
	(b) Lu, Z.; Li, T.; Mudshinge, S. R.; Xu, B.; Hammond, G. B. Chem. Rev. 2021, 121, 8452.
	(c) Zheng, Z.; Ma, X.; Cheng, X.; Zhao, K.; Gutman, K.; Li, T.; Zhang, L. Chem. Rev. 2021, 121, 8979.
	(d) Witzel, S.; Hashmi, A. S. K.; Xie, J. Chem. Rev. 2021, 121, 8868.
[2]	(a) Campeau, D.; Rayo, D. F. L.; Mansour, A.; Muratov, K.; Gagosz, F. Chem. Rev. 2021, 121, 8756.
	(b) Wang, T.; Hashmi, A. S. K. Chem. Rev. 2021, 121, 8948.
	(c) Dong, G.-Z.; Bao, M.; Xie, X.-D.; Jia, S.-K.; Hu, W.-H.; Xu, X.-F. Angew. Chem., nt. Ed. 2021, 60, 1992.
	(d) Bao, M.; Zhou, S.; Hu, W.; Xu, X. Chin. Chem. Lett. 2022, 33, 4969.
	(e) Hashmi, A. S. K. Catal. Today 2007, 122, 211.
[3]	(a) Wang, X.; Lv, R.; Li, X. Chem. Sci. 2024, 15, 936
	(b) Shi, Z.; Mao, W.; Yang, Z.; Sun, S.; Tung, C.-H.; Xu, Z. Chin. Chem. Lett. 2023, 34, 107488.
	(c) Wang, Z.; Chen, J.; Yu, L.; Zhang, C.; Rao, W.; Chan, P. W. H. Org. Lett. 2024, 26, 2635.
	(d) Alshreimi, A. S.; Zhang, G.; Shim, E. J.; Wink, D. J.; Anderson, L. L. ACS Catal. 2024, 14, 2229.
[4]	Bandini, M.; Eichholzer, A. Angew. Chem., Int. Ed. 2009, 48, 9533.
[5]	(a) Li, D.; Zang, W.; Bird, M. J.; Hyland, C. J. T.; Shi, M. Chem. Rev. 2021, 121, 8685.
	(b) Mato, M.; Franchino, A.; Garca-Morales, C.; Echavarren, A. M. Chem. Rev. 2021, 121, 8613.
	(c) Reyes, R. L.; Iwai, T.; Sawamura, M. Chem. Rev. 2021, 121, 8926.
[6]	(a) Gobé, V.; Retailleau, P.; Guinchard, X. Chem.-Eur. J. 2015, 21, 17587.
	(b) Fustero, S.; Miró, J.; Sánchez-Rosello, M.; del Pozo, C. Chem.-Eur. J. 2014, 20, 14126.
	(c) Rao, Q.; Zhang, Y.; Gu, X.-Y.; Liu, Y.-P.; Jiang, B.; Hao, W.-J. Catalysts 2023, 13, 1051.
	(d) Hao, M.-Y.; Zhang, Y.; Lin, N.; Fu, R.; Ji, X.-S.; Jiang, B.; Tu, S.-J.; Hao, W.-J. Chem. Commun. 2023, 59, 4032.
	(e) Qin, X.-Y.; Meng, F.-T.; Wang, M.; Tu, S.-J.; Hao, W.-J.; Wang, J.; Jiang, B. ACS Catal. 2021, 11, 6951.
[7]	(a) Simeonov, S. P.; Nunes, J. P. M.; Guerra, K.; Kurteva, V. B.; Afonso, C. A. M. Chem. Rev. 2016, 116, 5744.
	(b) Wagner, S.; Arce, R.; Murillo, R.; Terfloth, L.; Gasteiger, J.; Merfort, I. J. Med. Chem. 2008, 51, 1324.
	(c) Sepúlveda-Robles, O.; Espinoza-Gutiérrez, B.; Gomez-Verjan, J. C.; Guzmán-Gutiérrez, S. L.; Ita, M. D.; Silva-Miranda, M. C.; Espitia-Pinzón, I.; Fernández-Ramrez, F.; Herrera-Salazar, A.; Mata-Rocha, M.; Ortega-Hernández, A.; Reyes-Chilpa, R. Food Chem. Toxicol. 2015, 125, 55.
[8]	Wu, Z.-H.; Xie, Z.-H.; Wu, M.-L.; Li, X.-Q.; Li, W.-L.; Ding, W.-J.; She, Z.-G.; Li, C.-Y. J. Agric. Food Chem. 2018, 66, 5368.
[9]	Gokbulut, I.; Bilenler, T.; Karabulut, I. Int. J. Food Prop. 2013, 16, 1442.
[10]	(a) Klunder, A. J. H.; Zhu, J.; Zwanenburg, B. Chem. Rev. 1999, 99, 1163.
	(b) Touré, B. B.; Hall, D. G. Chem. Rev. 2009, 109, 4439.
	(c) Poplata, S.; Tröster, A.; Zou, Y.-Q.; Bach, T. Chem. Rev. 2016, 116, 9748.
[11]	(a) Zhang, L.-M.; Wang, S.-Z. J. Am. Chem. Soc. 2006, 128, 1442.
	(b) Chen, X.; Zhou, Y.; Hong, M.; Ling, Y.; Yin, D.; Wang, S.; Zhang, X.; Rao, W. Adv. Synth. Catal. 2018, 360, 3700.
	(c) Zhou, Y.; Chen, X.; Yin, D.-L.; Ling, Y.; Wang, S.-F.; Zhang, X.; Rao, W.-D. Eur. J. Org. Chem. 2019, 999.
	(d) Scarpi, D.; Favale, N.; Occhiato, E. G. J. Org. Chem. 2023, 88, 7015.
[12]	(a) Meng, F.-T.; Qin, X.-Y.; Li, J.; Zhang, T.-S.; Tu, S.-J.; Jiang, B.; Hao, W.-J. Chin. J. Chem. 2022, 40, 687.
	(b) Meng, F.-T.; Chen, J.-L.; Qin, X.-Y.; Zhang, T.-S.; Tu, S.-J.; Jiang, B.; Hao, W.-J. Org. Chem. Front. 2022, 9, 140.
	(c) Zhang, T.-S.; Li, J.; Sun, H.; Liu, S.; Li, J.; Chen, Y.; Hao, W.-J.; Jiang, B. Tetrahedron 2023, 147, 133661.
	(d) Meng, F.-T.; Wang, Y.-N.; Qin, X.-Y.; Li, S.-J.; Li, J.; Hao, W.-J.; Tu, S.-J.; Lan, Y.; Jiang, B. Nat. Commun. 2022, 13, 7393.
[13]	(a) Kumar, B.; Aga, M. A.; Mukherjee, D.; Chimni, S. S.; Taneja, S. C. Tetrahedron Lett. 2009, 50, 6236.
	(b) Ranu, B. C.; Saha, M. J. Org. Chem. 1994, 59, 8269.
	(c) Bar-toli, G.; Giovannini, R.; Giuliani, A.; Marcantoni, E.; Massac-cesi, M.; Melchiorre, P.; Paoletti, M.; Sambri, L. Eur. J. Org. Chem. 2006, 1476.
	(d) Stephens, J. R.; Butler, P. L.; Clow, C. H.; Oswald, M. C.; Smith, R. C.; Mohan, R. S. Eur. J. Org. Chem. 2003, 3827.
	(e) Sharma, A.; Ramos-Tomillero, I.; El-Faham, A.; Nicolas, E.; Rodriguez, H.; de la Torre, B. G.; Albericio, F. ChemistryOpen 2017, 6, 168.
[14]	(a) Williams, D. B. G.; Simelane, S. B.; Lawton, M.; Kinfe, H. H. Tetrahedron 2010, 66, 4573.
	(b) Falck, J. R.; Li, D. R.; Bejot, R.; Mioskowski, C. Tetrahedron Lett. 2006, 47, 5111.
	(c) Ochiai, M.; Sueda, T. Tetrahedron Lett. 2004, 45, 3557.
	(d) Sosnovsky, G. J. Org. Chem. 1960, 25, 874.
	(e) Durán-Peña, M. J.; Botubol-Ares, J. M.; Hanson, J. R.; Hernández-Galán, R.; Collado, I. G. Eur. J. Org. Chem. 2015, 633.

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.

[1]	马伊璇, 陈凯, 石航. 基于过渡金属π配位活化的芳香亲核取代反应研究进展[J]. 有机化学, 2025, 45(6): 2074-2085.
[2]	黄志友, 杨平, 何波, 欧文霞, 袁思雨. 吗啉磺酰胺化合物的设计、合成及其抑制大豆萌芽活性的研究[J]. 有机化学, 2024, 44(1): 309-315.
[3]	朱源, 陈乐园, 侯文彬, 李祎亮. 亲核氟源参与的芳环氟-18标记反应研究进展[J]. 有机化学, 2021, 41(5): 1774-1788.
[4]	韩满意, 潘虹, 姚紫云, 李琦. 四丁基溴化铵催化的布鲁克重排/烷基化反应[J]. 有机化学, 2020, 40(12): 4274-4283.
[5]	田禾, 吴景卫, 刘钰强, 谢亚非, 王建武, 赵桂龙. 含烷氧基取代的三唑类结构的尿酸转运体1抑制剂的高效合成方法[J]. 有机化学, 2017, 37(7): 1748-1756.
[6]	于海丰, 李铁纯, 廖沛球, 刁全平, 辛广, 侯冬岩. 酸度调控的3,3-二乙硫基丙烯酸酯的吲哚化反应[J]. 有机化学, 2014, 34(5): 956-961.
[7]	沈舒苏. 乙烯基碳上的亲核取代反应[J]. 有机化学, 2014, 34(12): 2448-2455.
[8]	吴利欢, 杨定乔. Friedl?nder反应合成新型喹啉衍生物及其结构表征[J]. 有机化学, 2010, 30(08): 1180-1184.
[9]	吕兆萍,张晓燕,杨红^{a. 微波辐射合成N-(2-氯-1-氧-5-吡啶甲基)二甲酰亚胺类化合物和生物活性研究[J]. 有机化学, 2008, 28(01): 89-93.}
[10]	邱早早,张欢欢,惠新平,许鹏飞王勤,杜宇平,杨洋. 3-杂环基硫取代-1,3,4,5-四氢-2-氧代-苯并氮杂衍生物的合成[J]. 有机化学, 2007, 27(05): 607-618.
[11]	李立清,王晓刚,郭三霞,刘重洋,何益波. 一锅法有效合成氨基甲酸酯类化合物[J]. 有机化学, 2007, 27(04): 519-523.
[12]	周智明岳纪炜,沈宁,余从煊. 硝基芳环和硝基杂芳环中氢的替代亲核取代[J]. 有机化学, 2007, 27(01): 17-23.
[13]	盖景刚, 任译. 硫原子上亲核取代反应的密度泛函理论研究[J]. 有机化学, 2004, 24(10): 1267-1270.
[14]	邹新琢*,井火田敏一,隈弘夫. 多氯代吗啉硝基苯的高压合成与晶体结构[J]. 有机化学, 2001, 21(5): 372-375.
[15]	徐善生,钟秀斌,周秀中. 四甲基二硅桥连双(四甲基环戊二烯基)四羰基二铁的反应性[J]. 有机化学, 1996, 16(4): 364-366.

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

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 7

参考文献 14

相关文章 15

编辑推荐

相关统计

本文评价