铜催化烯醇硅醚与芳基亚磺酸钠合成β-酮砜的研究

doi:10.6023/cjoc202304029

摘要/Abstract

β-酮砜是一类重要的含硫化合物和有机合成中间体, 被广泛应用于天然产物及许多重要有机化合物的构筑. 开发了一种溴化铜催化烯醇硅醚与芳基亚磺酸钠快速合成β-酮砜的方法, 具有操作简单、条件温和和反应时间短等优点.

β-Keto sulfones are an important group of sulfur-containing compounds and intermediates for organic synthesis, which are widely used in the construction of natural products and various important organic compounds. A method for the rapid synthesis of β-keto sulfones catalyzed by copper bromide from enol silyl ether and sodium arylsulfinates is developed, which has the advantages of simple operation, mild conditions and short reaction time.

Key words: β-keto sulfone, copper catalysis, enol silyl ether, sodium arylsulfinate

引用此文

许力, 吕兰兰, 王香善. 铜催化烯醇硅醚与芳基亚磺酸钠合成β-酮砜的研究[J]. 有机化学, 2023, 43(10): 3644-3651.

Li Xu, Lanlan Lü, Xiangshan Wang. Copper-Catalyzed Synthesis of β-Keto Sulfones from Enol Silyl Ether and Sodium Arylsulfinates[J]. Chinese Journal of Organic Chemistry, 2023, 43(10): 3644-3651.

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图/表 5

图式1. 部分过渡金属催化亚磺酸钠合成β-酮砜的方法

Scheme 1. A partial transition metal-catalyzed sodium sulfite synthesis of β-keto sulfones

Entry	[M]	Solvent	Temp./℃	Yield^b/%
1	CuBr₂	DMSO	80	56
2	CuBr₂	DMF	80	24
3	CuBr₂	1,4-Dioxane	80	8
4	CuBr₂	Toluene	80	20
5	CuBr₂	MeCN	80	12
6	CuBr₂	DCE	80	27
7	CuCl₂	DMSO	80	30
8	Cu(OTf)₂	DMSO	80	29
9	Cu(OAc)₂	DMSO	80	51
10	CuCl	DMSO	80	42
11	CuBr	DMSO	80	45
12	Cu powder	DMSO	80	18
13	Pd(OAc)₂	DMSO	80	0
14	Ag₂CO₃	DMSO	80	0
15	CuBr₂	DMSO	100	66
16	CuBr₂	DMSO	60	79
17	CuBr₂	DMSO	40	83
18	CuBr₂	DMSO	rt	89
19^c	CuBr₂	DMSO	rt	67
20^d	CuBr₂	DMSO	rt	13

表1. 化合物3a的最佳条件筛选a

Table 1. Screening of optimal conditions for 3a

表2. 烯醇硅醚的底物拓展a,b

Table 2. Scope of enol silyl ether

图式2. 放大量实验及进一步衍生化

Scheme 2. Gram-scale synthesis and further derivatization

图式3. 控制实验和可能的反应机理

Scheme 3. Control experiments and possible mechanism

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