Brønsted酸催化α-烯丙基-1,3-二酮的逆Claisen反应

doi:10.6023/cjoc202411023

有机化学 ›› 2025, Vol. 45 ›› Issue (7): 2461-2468.DOI: 10.6023/cjoc202411023 上一篇下一篇

研究论文

Brønsted酸催化α-烯丙基-1,3-二酮的逆Claisen反应

王亮霞, 徐长明^*()

兰州交通大学化学化工学院兰州 730070

收稿日期:2025-01-03 修回日期:2025-01-23 发布日期:2025-02-27
通讯作者: 徐长明
基金资助:
国家自然科学基金(22061025); 甘肃省自然科学基金(20JR10RA220); 兰州交通大学“百人计划”基金资助项目

Retro-Claisen Reaction of α-Allyl-1,3-diketones Catalyzed by Brønsted Acid

Liangxia Wang, Changming Xu^*()

School of Chemistry and Chemical Engineering, Lanzhou Jiaotong University, Lanzhou 730070

Received:2025-01-03 Revised:2025-01-23 Published:2025-02-27
Contact: Changming Xu
Supported by:
National Natural Science Foundation of China(22061025); Natural Science Foundation of Gansu Province(20JR10RA220); Foundation of a Hundred Youth Talents Training Program of Lanzhou Jiaotong University

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摘要/Abstract

报道了Brønsted酸催化α-烯丙基-1,3-二酮与H₂O的逆Claisen反应, 以中等的产率得到了一系列酮酯类化合物, 为合成γ-羟基酮类化合物提供了一种新方法. 该反应无过渡金属参与, 反应条件温和, 操作简单, 提供了一种新的逆Claisen反应途径. ¹⁸O同位素标记实验表明γ-羟基酮中的羟基氧来自于H₂O.

关键词: 逆Claisen反应, α-烯丙基-1,3-二酮, Brønsted酸, 半缩酮

Brønsted acid catalyzed retro-Claisen reaction of α-allyl-1,3-diketones with H₂O was reported, giving a series of ketoester compounds with moderate yield, which provided a new method for the synthesis of γ-hydroxy ketones. This reaction features transition metal-free, mild reaction conditions and simple operation, and represents a novel retro-Claisen reaction pathway. The ¹⁸O isotope labeling experiment confirmed that the oxygen atom in the hydroxyl group of γ-hydroxy ketone came from water.

Key words: retro-Claisen reaction, α-allyl-1,3-diketone, Brønsted-acid, hemiketal

引用此文

王亮霞, 徐长明. Brønsted酸催化α-烯丙基-1,3-二酮的逆Claisen反应[J]. 有机化学, 2025, 45(7): 2461-2468.

Liangxia Wang, Changming Xu. Retro-Claisen Reaction of α-Allyl-1,3-diketones Catalyzed by Brønsted Acid[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2461-2468.

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图/表 7

图式1. 1,3-二羰基化合物的逆Claisen反应

Scheme 1. Retro-Claisen reaction of 1,3-dicarbonyl compounds

Entry	Acid	H₂O (equiv.)	Solvent	Time/h	Conversion/%	Yield/%
Entry	Acid	H₂O (equiv.)	Solvent	Time/h	Conversion/%	2a	3
1	MsOH	H₂O (2.0)	DCE	43	62	32	10
2	TFA	H₂O (2.0)	DCE	28	0	0	0
3	p-TSA	H₂O (2.0)	DCE	14	0	0	0
4	TfOH	H₂O (2.0)	DCE	24	66	52	Trace
5	Tf₂NH	H₂O (2.0)	DCE	24	53	25	9
6	H₂SO₄	H₂O (2.0)	DCE	24	0	0	0
7	HNO₃	H₂O (2.0)	DCE	24	0	0	0
8	TfOH	H₂O (1.0)	DCE	27	60	48	Trace
9	TfOH	H₂O (4.0)	DCE	30	49	38	Trace
10	TfOH	H₂O (8.0)	DCE	48	47	36	Trace
11	TfOH	—	DCE	48	0	0	0
12	TfOH	H₂O (2.0)	Tol	36	58	32	8
13	TfOH	H₂O (2.0)	THF	36	0	0	0
14	TfOH	H₂O (2.0)	MeCN	36	64	37	8
15	TfOH	H₂O (2.0)	PhH	12	72	54	Trace
16	TfOH	H₂O (2.0)	CHCl₃	36	56	43	Trace
17	TfOH	H₂O (2.0)	CH₂Cl₂	24	31	Trace	27

表1. 反应条件的优化a,b

Table 1. Optimization of the reaction conditions

表2. α-烯丙基-1,3-二酮底物范围a,b,c

Table 2. Substrate scope of α-allyl-1,3-diketones

图式2. α-烯丙基-1,3-二酮的环化反应

Scheme 2. Cyclization reactions of α-allyl-1,3-diketones Unless otherwise noted, all reactions were carried out using 1a (0.2 mmol) and H2O (0.4 mmol) in benzene (1.0 mL) with 20 mol% of TfOH.

图式3. 2a的衍生实验

Scheme 3. Derivative experiments of 2a

图式4. 同位素标记实验

Scheme 4. Isotope labeling experiment

图式5. 可能的反应机理

Scheme 5. Possible reaction mechanism

参考文献 28

[1]	(a) Han W. C.; Takahashi K.; Cook J. M.; Weiss U.; Silverton J. V. J. Am. Chem. Soc. 1982, 104, 318.
	(b) Grogan G.; Graf J.; Jones A.; Parsons S.; Turner N. J.; Flitsch S. L. Angew. Chem., Int. Ed. 2001, 113, 1145.
	(c) Kawata A.; Takata K.; Kuninobu Y.; Takai K. Angew. Chem., Int. Ed. 2007, 46, 7793.
[2]	For a selected example, see: Grenning,A. J.; Tunge, J. A. J. Am. Chem. Soc. 2011, 133, 14785.
[3]	Roudier M.; Constantieux T.; Quintard A.; Rodriguez J. Org. Lett. 2014, 16, 2802. doi: 10.1021/ol500821c pmid: 24849709
[4]	(a) Zhu Y.; Zhang L.; Luo S. J. Am. Chem. Soc. 2016, 138, 3978.
	(b) Han Y.; Zhang L.; Luo S. Org. Lett. 2019, 21, 7258.
	(c) Han Y.; Zhang L.; Luo S. Org. Lett. 2022, 24, 1752.
	(d) For a similar example, see: Biswas,R. G.; Ray, S. K.; Unhale, R. A.; Singh, V. K. Org. Lett. 2021, 23, 6504.
[5]	Yi Z. Y.; Xiao L.; Chang X.; Dong X. Q.; Wang C. J. Am. Chem. Soc. 2022, 144, 20025.
[6]	Chawla R.; Singh A. K.; Yadav L. D. S. Tetrahedron Lett. 2012, 53, 3382.
[7]	Anh To T.; Pei C.; Koenigs R. M.; Vinh Nguyen T. Angew. Chem., Int. Ed. 2022, 61, e202117366.
[8]	Miao M.; Jin M.; Chen P.; Wang L.; Zhang S.; Ren H. Org. Lett. 2019, 21, 5957.
[9]	Chacko S.; Kalita M.; Ramapanicker R. Tetrahedron: Asymmetry. 2015, 26, 623.
[10]	Clive D. L.; Wang J. J. Org. Chem. 2004, 69, 2773.
[11]	González Miera G.; Bermejo López A.; Martínez‐Castro E.; Norrby P. O.; Martín‐Matute B. Chem.-Eur. J. 2019, 25, 2631. doi: 10.1002/chem.201805460 pmid: 30475410
[12]	Cho H.; Madden R.; Nisanci B.; Török B. Green Chem. 2015, 17, 1088.
[13]	Handy S.; Lavender K. Tetrahedron Lett. 2013, 54, 4377.
[14]	Kaleta Z.; Makowski B. T.; Soós T.; Dembinski R. Org. Lett. 2006, 8, 1625.
[15]	Kise N.; Shiozawa Y.; Ueda N. Tetrahedron. 2007, 63, 5415.
[16]	Rigotti T.; Bach T. Org. Lett. 2022, 24, 8821.
[17]	Peloquin A. J.; Stone R. L.; Avila S. E.; Rudico E. R.; Horn C. B.; Gardner K. A.; Ball D. W.; Johnson J. E. B.; Iacono S. T.; Balaich G. J. J. Org. Chem. 2012, 77, 6371. doi: 10.1021/jo301101x pmid: 22747487
[18]	(a) Quan J.; He X.; Yan X.; Li X.; Xu X. Chin. J. Org. Chem. 2020, 40, 1033 (in Chinese). pmid: 30264840
	全积宁, 何小雪, 严新焕, 李小青, 许响生, 有机化学, 2020, 40, 1033. pmid: 30264840
	(b) Liu J.; Liu Q. Y.; Fang X. X.; Liu G. Q.; Ling Y. Org. Biomol. Chem. 2018, 16, 7454. doi: 10.1039/c8ob02161a pmid: 30264840
	(c) Zdvizhkov A. T.; Terent’ev A. O.; Radulov P. S.; Novikov R. A.; Tafeenko V. A.; Chernyshev V. V.; Ilovaisky A. I.; Levitsky D. O.; Fleury F.; Nikishin G. I. Tetrahedron Lett. 2016, 57, 949. pmid: 30264840
[19]	Maity R.; Gharui C.; Sil A. K.; Pan S. C. Org. Lett. 2017, 19, 662.
[20]	Yang N. Y.; Li Z. L.; Ye L.; Tan B.; Liu X. Y. Chem. Commun. 2016, 52, 9052.
[21]	Guan Z.; Wang Y.; Wang H.; Huang Y.; Wang S.; Tang H.; Zhang H.; Lei A. Green Chem. 2019, 21, 4976.
[22]	Kanno S.; Kakiuchi F.; Kochi T. J. Am. Chem. Soc. 2021, 143, 19275.
[23]	Percy J. M.; McCarter A. W.; Sewell A. L.; Sloan N.; Kennedy A. R.; Hirst D. J. Chem.-Eur. J. 2015, 21, 19119.
[24]	Sau M. C.; Mandal S.; Bhattacharjee M. RSC Adv. 2021, 11, 9235.
[25]	Li B.; Wang J.; Wang J.; Zhao Y. Chem. Asian J. 2023, 18, e202300030.
[26]	Princival J. L.; Dos Santos A. A.; Comasseto J. V. Tetrahedron Lett. 2009, 50, 6368.
[27]	Suzuki H.; Yoshioka S.; Igesaka A.; Nishioka H.; Takeuchi Y. Tetrahedron 2013, 69, 6399.
[28]	Avery T. D.; Taylor D. K.; Tiekink E. R. J. Org. Chem. 2000, 65, 5531. pmid: 10970292

Brønsted酸催化α-烯丙基-1,3-二酮的逆Claisen反应

Retro-Claisen Reaction of α-Allyl-1,3-diketones Catalyzed by Brønsted Acid

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