氮杂环卡宾(NHC)催化水杨醛与吡唑啉酮-4,5-二酮的[4＋2]环加成反应高效构建螺缩酮-吡唑啉酮化合物

doi:10.6023/cjoc202406005

有机化学 ›› 2025, Vol. 45 ›› Issue (1): 267-275.DOI: 10.6023/cjoc202406005 上一篇下一篇

研究论文

氮杂环卡宾(NHC)催化水杨醛与吡唑啉酮-4,5-二酮的[4＋2]环加成反应高效构建螺缩酮-吡唑啉酮化合物

王晓梅, 刘岩, 李师伍^*(), 赵志飞^*()

石河子大学化学化工学院化工绿色过程省部共建国家重点实验室培育基地新疆石河子 832000

收稿日期:2024-06-04 修回日期:2024-07-10 发布日期:2024-08-23
基金资助:
石河子大学(2022ZK003); 石河子大学(RCZK202001); 新疆维吾尔自治区“天池英才”引进(CZ002737)

N-Heterocyclic Carbene-Catalyzed [4＋2] Cycloaddition of Salicylaldehydes with Pyrazole-4,5-diones for the Synthesis of Spiroketal-Pyrazolones

Xiaomei Wang, Yan Liu, Shiwu Li(), Zhifei Zhao()

State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832000

Received:2024-06-04 Revised:2024-07-10 Published:2024-08-23
Contact: *E-mail: zhaozf@shzu.edu.cn; lishiwu@shzu.edu.cn
Supported by:
Shihezi University(2022ZK003); Shihezi University(RCZK202001); Tianchi Talent Project of Xinjiang Uygur Autonomous Region(CZ002737)

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摘要/Abstract

利用氮杂环卡宾(NHC)催化水杨醛与吡唑啉酮-4,5-二酮的[4＋2]环加成反应直接合成了缩醛的两个氧在同一环内的螺缩酮-吡唑酮化合物. 该反应的底物有很好的普适性, 并获得了中等到优异的产率(最高达到98%). 该方法反应条件温和, 操作简便, 为合成含吡唑啉酮的高官能团化的螺缩酮化合物提供了新的合成方法学. 此外, 克级反应和衍生化转化也能顺利进行.

关键词: 氮杂环卡宾, 环加成, 水杨醛, 吡唑啉酮-4,5-二酮, 螺缩酮-吡唑啉酮

The first efficiently N-heterocyclic carbene-catalyzed [4＋2] cycloaddition of salicylaldehydes and pyrazole-4,5- diones to directly synthesis of spiro-ketal-pyrazolones bearing both oxygens of the ketal unit in the same ring was disclosed. This reaction was qualified with broad substrate scope, achieving moderate to excellent yield (up to 98%). This method has mild reaction conditions and simple operation, providing a new attractive strategy for the practical syntheses of multi- functionalized spiroketals including pyrazolone structures with mild reaction condition and operational simplicity. Furthermore, the gram scale and derivative transformations have also been achieved.

Key words: N-heterocyclic carbene, cycloaddition, salicylaldehyde, pyrazole-4,5-dione, spiro-ketal-pyrazolone

引用此文

王晓梅, 刘岩, 李师伍, 赵志飞. 氮杂环卡宾(NHC)催化水杨醛与吡唑啉酮-4,5-二酮的[4＋2]环加成反应高效构建螺缩酮-吡唑啉酮化合物[J]. 有机化学, 2025, 45(1): 267-275.

Xiaomei Wang, Yan Liu, Shiwu Li, Zhifei Zhao. N-Heterocyclic Carbene-Catalyzed [4＋2] Cycloaddition of Salicylaldehydes with Pyrazole-4,5-diones for the Synthesis of Spiroketal-Pyrazolones[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 267-275.

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Entry	Catalyst	Base (mol%)	Solvent	T/℃	Yield^b/%
1	A1	Et₃N (150)	THF	25	49
2	A2	Et₃N (150)	THF	25	46
3	A3	Et₃N (150)	THF	25	73
4	A4	Et₃N (150)	THF	25	16
5	A5	Et₃N (150)	THF	25	21
6	A6	Et₃N (150)	THF	25	Trace
7	A7	Et₃N (150)	THF	25	Trace
8	A3	Et₃N (50)	THF	25	74
9	A3	DBU (50)	THF	25	68
10	A3	Cs₂CO₃ (50)	THF	25	71
11	A3	NaOH (50)	THF	25	69
12	A3	^tBuOK (50)	THF	25	79
13	A3	KOH (50)	THF	25	82
14	A3	KOH (50)	DCM	25	65
15	A3	KOH (50)	EtOAc	25	63
16	A3	KOH (50)	THF	30	54
17	A3	KOH (50)	THF	－10	66

Entry	Catalyst	Base (mol%)	Solvent	T/℃	Yield^b/%
1	A1	Et₃N (150)	THF	25	49
2	A2	Et₃N (150)	THF	25	46
3	A3	Et₃N (150)	THF	25	73
4	A4	Et₃N (150)	THF	25	16
5	A5	Et₃N (150)	THF	25	21
6	A6	Et₃N (150)	THF	25	Trace
7	A7	Et₃N (150)	THF	25	Trace
8	A3	Et₃N (50)	THF	25	74
9	A3	DBU (50)	THF	25	68
10	A3	Cs₂CO₃ (50)	THF	25	71
11	A3	NaOH (50)	THF	25	69
12	A3	^tBuOK (50)	THF	25	79
13	A3	KOH (50)	THF	25	82
14	A3	KOH (50)	DCM	25	65
15	A3	KOH (50)	EtOAc	25	63
16	A3	KOH (50)	THF	30	54
17	A3	KOH (50)	THF	－10	66

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氮杂环卡宾(NHC)催化水杨醛与吡唑啉酮-4,5-二酮的[4＋2]环加成反应高效构建螺缩酮-吡唑啉酮化合物

N-Heterocyclic Carbene-Catalyzed [4＋2] Cycloaddition of Salicylaldehydes with Pyrazole-4,5-diones for the Synthesis of Spiroketal-Pyrazolones

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