光促进铜催化异噁唑酮与醇反应合成异肟酸酯

doi:10.6023/cjoc202504030

有机化学 ›› 2025, Vol. 45 ›› Issue (12): 4346-4353.DOI: 10.6023/cjoc202504030 上一篇下一篇

研究论文

光促进铜催化异噁唑酮与醇反应合成异肟酸酯

冯天惠^†, 任志强^†, 高甜莉, 韩波, 郭蕊丽, 马豪杰, 王记江, 张玉琦^*()

延安大学化学化工学院化学反应工程陕西省重点实验室化学反应工程陕西省重点实验室陕西延安 716000

收稿日期:2025-04-28 修回日期:2025-07-10 发布日期:2025-08-26
通讯作者: 张玉琦
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(22301264); 陕西省自然科学基础研究计划(2023-JC-QN-0135); 陕西省自然科学基础研究计划(2024-JC-YBQN-0083); 延安大学研究(YAU202407417)

Visible-Light-Driven Copper-Catalyzed the Synthesis of Hydroxamates with Dioxazolones and Methanol

Tianhui Feng, Zhiqiang Ren, Tianli Gao, Bo Han, Ruili Guo, Haojie Ma, Jijiang Wang, Yuqi Zhang^*()

Shaanxi Key Laboratory of Chemical Reaction Engineering, School of Chemistry and Chemical Engineering, Yan'an University, Yan'an, Shaanxi 716000

Received:2025-04-28 Revised:2025-07-10 Published:2025-08-26
Contact: Yuqi Zhang
About author:
^† The authors contributed equally to this work
Supported by:
National Natural Science Foundation of China(22301264); Natural Science Basic Research Program of Shaanxi Province(2023-JC-QN-0135); Natural Science Basic Research Program of Shaanxi Province(2024-JC-YBQN-0083); Research Program of Yan'an University(YAU202407417)

文章分享

1. 254346S.pdf(3369KB)

摘要/Abstract

高原子经济性是构建功能有机分子的追求目标, 也是绿色化学的核心内容之一. 报道了一种可见光促进铜催化异噁唑酮与醇反应合成异肟酸酯. 该反应具有高原子经济性, 催化剂负载量低至5 mol%, 反应条件温和, 底物范围广泛且产率优异. 机理研究表明, C—O键的断裂可能参与了反应过程.

关键词: 高原子经济性, 可见光驱动, 异噁唑酮, 羟肟酸酯

High atomic economy is an aspirational target of the construction functional organic molecules, which is one of the core contents of green chemistry. The visible-light-driven copper-catalyzed synthesis of hydroxamates from dioxazolones has been reported. This reaction possesses high atom economy, a catalyst loading as low as 5 mol%, mild reaction conditions, and a broad substrate scope with excellent yields. A mechanistic study reveals that cleavage of C—O bond might be involved in the reaction.

Key words: high atomic economy, visible-light-driven, dioxazolones, hydroxamates

引用此文

冯天惠, 任志强, 高甜莉, 韩波, 郭蕊丽, 马豪杰, 王记江, 张玉琦. 光促进铜催化异噁唑酮与醇反应合成异肟酸酯[J]. 有机化学, 2025, 45(12): 4346-4353.

Tianhui Feng, Zhiqiang Ren, Tianli Gao, Bo Han, Ruili Guo, Haojie Ma, Jijiang Wang, Yuqi Zhang. Visible-Light-Driven Copper-Catalyzed the Synthesis of Hydroxamates with Dioxazolones and Methanol[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4346-4353.

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

分享此文

图/表 8

Figure 1. Structures of representative hydroxamates

Scheme 1. Synthetic strategy of hydroxamic acid esters

Entry	Light	Cu catalyst	Solvent	Yield^b/%
1	Green	Cu(OAc)₂	CHCl₃	88
2	Green	No	CHCl₃	61
3	No	Cu(OAc)₂	CHCl₃	No
4	Green	CuBr•Me₂S	CHCl₃	26
5	Green	Cu(MeCN)₄PF₆	CHCl₃	34
6	Green	CuCl	CHCl₃	13
7	Green	CuCN	CHCl₃	Trace
8	Green	CuI	CHCl₃	Trace
9	Green	Cu(OAc)₂	CH₂Cl₂	64
10	Green	Cu(OAc)₂	ClCH₂CH₂Cl	37
11	Purple	Cu(OAc)₂	CHCl₃	78
12	Blue	Cu(OAc)₂	CHCl₃	71
13	White	Cu(OAc)₂	CHCl₃	65

Table 1. Screening of reaction conditionsa

Scheme 2. Scope with various dioxazolones and alcohols

Scheme 3. Mechanistic studies (i) Experiment of radical capture; (ii) and (iii) experiment of nitrogen capture; (iv) and (v) deuterium exchange experiment; (vi) KIE experiment

Figure 2. Mechanistic studies (a) EPR experiment of Cu(Ⅱ); (b) EPR experiment of radical response; (c) light on-off experiment; (d) UV-vis absorption spectra of methanol

Scheme 4. Possible mechanism for visible-light-driven copper- catalyzed C—O bond cleavage

Scheme 5. Broaden scale synthesis of 3a Reaction conditions: 1a (6.2 mmol), MeOH (10 mL), Cu(OAc)2 (5 mol%), CHCl3 (20 mL), at room temperature, under 50 W Green LED irradiation for 24 h, yield of isolated product.

参考文献 9

[1]	Chigan J.-Z.; Li J.-Q.; Ding H.-H.; Xu Y.-S.; Lu L.; Cheng C.; Yang K.-W. Chem. Biol. Drug Des. 2022, 99, 362. doi: 10.1111/cbdd.v99.2
[2]	Malico A. A.; Dave K.; Adediran S. A.; Pratt R. F. Bioorg. Med. Chem. 2019, 27, 1430. doi: 10.1016/j.bmc.2019.02.023
[3]	(a) Wu X.-R.; Chen W.-Y.; Liu L.; Yang K.-W. Eur. J. Med. Chem. 2024, 265, 116055. doi: 10.1016/j.ejmech.2023.116055
	(b) Rajendra G.; Miller M. J. Tetrahedron Lett. 1985, 26, 5385. doi: 10.1016/S0040-4039(00)98214-5
	(c) Carosso S.; Miller M. J. Bioorg. Med. Chem. 2015, 23, 6138.
	(d) Rajendra G. M.; Miller J. Tetrahedron Lett. 1987, 28, 6257. doi: 10.1016/S0040-4039(01)91346-2
	(e) Lin J. M.; Koch K. F.; Fowler W. J. Org. Chem. 1986, 51, 167. doi: 10.1021/jo00352a008
	(f) Bulychev A.; O'Brien M. E.; Massova I.; Teng M.; Gibson T. A.; Miller M. J.; Mobashery S. J. Am. Chem. Soc. 1995, 117, 5938. doi: 10.1021/ja00127a005
[4]	(a) Wang S.-B.; Gu Q.; You S.-L. J. Catal. 2018, 361, 393. doi: 10.1016/j.jcat.2018.03.007 pmid: 33753917
	(b) Lyu X.; Zhang J.; Kim D.; Seo S.; Chang S. J. Am. Chem. Soc. 2021, 143, 5867. doi: 10.1021/jacs.1c01138 pmid: 33753917
	(c) Kim S.; Jeoung D.; Kim K.; Lee S. B.; Lee S. H. Eur. J. Org. Chem. 2020, 2020, 7134. doi: 10.1002/ejoc.v2020.46 pmid: 33753917
	(d) Ma Q.; Yu X.; Lai R.; Lv S.; Zhang C.; Wang X.; Wang Q.; Wu Y. ChemSusChem 2018, 11, 3672. doi: 10.1002/cssc.v11.20 pmid: 33753917
	(e) Atkin L.; Priebbenow D. L. Angew. Chem. Int. Ed. 2023, 62, e202302175. doi: 10.1002/anie.v62.23 pmid: 33753917
	(f) Yang J.; Hu X.; Liu Z.; Li X.; Dong Y.; Liu G. Chem. Commun. 2019, 55, 13840. doi: 10.1039/C9CC07173C pmid: 33753917
	(g) Jeon B.; Yeon U.; Son J.-Y.; Lee P. H. Org. Lett. 2016, 18, 4610. doi: 10.1021/acs.orglett.6b02250 pmid: 33753917
	(h) Jeon M.; Mishra N. K.; De U.; Sharma S.; Oh Y.; Choi M.; Jo H.; Sachan R.; Kim H. S.; Kim I. S. J. Org. Chem. 2016, 81, 9878. doi: 10.1021/acs.joc.6b02020 pmid: 33753917
	(i) Kong L. X.; Han P.; Hu F.; Li W. X. Chem. Commun. 2023, 59, 6690. doi: 10.1039/D3CC01666H pmid: 33753917
	(j) Han G. U.; Shin S.; Baek Y.; Kim D.; Lee K.; Kim J. G.; Lee P. H. Org. Lett. 2021, 23, 8622. doi: 10.1021/acs.orglett.1c03336 pmid: 33753917
	(k) Baek Y.; Kim S.; Son J.-Y.; Lee K.; Kim D.; Lee P. H. ACS Catal. 2019, 9, 10418. doi: 10.1021/acscatal.9b03380 pmid: 33753917
	(l) Samanta S.; Mondal S.; Ghosh D.; Hajra A. Org. Lett. 2019, 21, 4905. doi: 10.1021/acs.orglett.9b01832 pmid: 33753917
	(m) Wagner-Carlberg N.; Rovis T. J. Am. Chem. Soc. 2022, 144, 22426. doi: 10.1021/jacs.2c10552 pmid: 33753917
	(n) Chen Y.; Zhang R.; Peng Q.; Xu L.; Pan X. Chem. Asian J. 2017, 12, 2804. doi: 10.1002/asia.v12.21 pmid: 33753917
	(o) Lei H.; Rovis T. J. Am. Chem. Soc. 2019, 141, 2268. doi: 10.1021/jacs.9b00237 pmid: 33753917
	(p) Knecht T.; Mondal S.; Ye J.-H.; Das M.; Glorius F. Angew. Chem., Int. Ed. 2019, 58, 7117. doi: 10.1002/anie.v58.21 pmid: 33753917
	(q) Chen C.; Shi C.; Yang Y.; Zhou B. Chem. Sci. 2020, 11, 12124. doi: 10.1039/D0SC04007J pmid: 33753917
	(r) Dhiman A. K.; Thakur A.; Kumar I.; Kumar R.; Sharma U. J. Org. Chem. 2020, 85, 9244. doi: 10.1021/acs.joc.0c01237 pmid: 33753917
	(s) Park Y.; Park K.; Kim J. G.; Chang S. J. Am. Chem. Soc. 2015, 137, 4534. doi: 10.1021/jacs.5b01324 pmid: 33753917
	(t) Tang J.-J.; Yan N.; Zhang Y.; Wang Y.; Bao M.; Yu X. Green Chem. 2023, 25, 7529. doi: 10.1039/D3GC02479B pmid: 33753917
	(u) Wang H.; Jung H.; Song F.; Zhu S.; Bai Z.; Chen D.; He G.; Chang S.; Chen G. Nat. Chem. 2021, 13, 378. doi: 10.1038/s41557-021-00650-0 pmid: 33753917
	(v) Zhou Y.; Engl O. D.; Bandar J. S.; Chant E. D.; Buchwald S. L. Angew. Chem. Int. Ed. 2018, 57, 6672. doi: 10.1002/anie.v57.22 pmid: 33753917
[5]	(a) Shaw M. H.; Twilton J.; MacMillan D. W. C. J. Org. Chem. 2016, 81, 6898. doi: 10.1021/acs.joc.6b01449 pmid: 27625298
	(b) Beeler A. B. Chem. Rev. 2016, 116, 9629. doi: 10.1021/acs.chemrev.6b00378 pmid: 27625298
	(c) Liu Q.; Wu L.-Z. Natl. Sci. Rev. 2017, 4, 359. doi: 10.1093/nsr/nwx039 pmid: 27625298
[6]	(a) Zhuo J.; Zhu C.; Wu J.; Li Z.; Li C. J. Am. Chem. Soc. 2022, 144, 99. doi: 10.1021/jacs.1c11623 pmid: 10987925
	(b) Ali G.; VanNatta P. E.; Ramirez D. A.; Light K. M.; Kieber- Emmons M. T. J. Am. Chem. Soc. 2017, 139, 18448. doi: 10.1021/jacs.7b10833 pmid: 10987925
	(c) Fields J. D.; Kropp P. J. J. Org. Chem. 2000, 65, 5937. pmid: 10987925
[7]	(a) Tang J.-J.; Yu X.; Wang Y.; Yamamoto Y.; Bao M. Angew. Chem. Int. Ed. 2021, 60, 16426. doi: 10.1002/anie.v60.30
	(b) Zhang Q.; Liu S.; Xie Y.; Du T.; Wang S.; Guan J.; Li J.; Tang H.; Zhou Z. Eur. J. Org. Chem. 2024, 27, e202400440.
	(c) Park J.; Unnikrishnan K. A.; Park Y.; Kim M.; Reidl T. W.; Kuniyil R.; Son J. Adv. Synth. Catal. 2023, 365, 4495. doi: 10.1002/adsc.v365.24
[8]	(a) Karunananda M. K.; Mankad N. P. Organometallics 2017, 36, 220. doi: 10.1021/acs.organomet.6b00356
	(b) Wakita Y.; Kobayashi T.; Maeda M.; Kojima M. Chem. Pharm. Bull. 1982, 30, 3395. doi: 10.1248/cpb.30.3395
	(c) Wakita Y.; Noma S.; Maeda M.; Kojima M. J. Organomet. Chem. 1985, 297, 379. doi: 10.1016/0022-328X(85)80441-1
	(d) McManus C.; Crumptona A. E.; Aldridge S. Chem. Commun. 2022, 58, 8274. doi: 10.1039/D2CC02578G
[9]	Huang J.; Li X.; Wen H.; Ouyang L.; Luo N.; Liao J.; Luo R. ACS Omega 2021, 6, 11740. doi: 10.1021/acsomega.1c01083

光促进铜催化异噁唑酮与醇反应合成异肟酸酯

Visible-Light-Driven Copper-Catalyzed the Synthesis of Hydroxamates with Dioxazolones and Methanol

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 8

参考文献 9

相关文章 3

编辑推荐

相关统计

本文评价

[1]	贺重隆, 周有康, 段新华, 刘乐. 官能团迁移策略在光驱动不饱和烃双官能团化中的应用[J]. 有机化学, 2025, 45(5): 1478-1508.
[2]	刘思展, 崔明月, 王博文, 胡春梅, 郑莹莹, 李晶, 徐学涛, 王震, 王少华. 三乙胺促进的环丙烯酮和α-卤代异羟肟酸酯的环化反应合成多取代6H-1,3-噁嗪-6-酮[J]. 有机化学, 2021, 41(4): 1622-1630.
[3]	张广良,李耀先,张锁秦,夏柏莹,高飞飞. 4,4-二甲基-3-异噁唑酮衍生物的合成与表征[J]. 有机化学, 2005, 25(07): 800-804.