无过渡金属条件下二芳基硒化合物的合成

doi:10.6023/cjoc202303011

摘要/Abstract

报道了一种以二芳基硒醚为硒基来源, K₂S₂O₈为氧化剂, 在无过渡金属条件下对N-芳基酰胺化合物的C(sp²)—H键直接官能化, 合成了系列二芳基硒化合物的方法. 机理研究表明, 该反应经过单电子转移的自由基历程, 中间体的稳定性决定了反应的选择性. 该反应官能团兼容性好, 位点选择性强, 操作简便, 成本低廉, 是一种实用的二芳基硒化合物的合成方法.

关键词: 无过渡金属催化, C—Se键构建, 区域选择性

A series of diaryl selenium compounds were synthetized from N-arylamide compounds and diphenyl diselenide, using K₂S₂O₈ as oxidant without any transition metal catalyst. Mechanistic studies reveal that the reaction proceeds a single-electron transfer radical process. The dominant products are o-substituted and p-substituted product, depending on the stability of intermediates. The synthetic reaction exhibits some outstanding advantages, such as substrate tolerance, high regioselectivity, convenience and low-price.

Key words: transition metal-free, construction of C—Se bond, regional selectivity

引用此文

孙婧, 张萌萌, 锅小龙, 王琪, 王陆瑶. 无过渡金属条件下二芳基硒化合物的合成[J]. 有机化学, 2023, 43(12): 4251-4260.

Jing Sun, Mengmeng Zhang, Xiaolong Guo, Qi Wang, Luyao Wang. Synthesis of Diaryl Selenium Compounds without Transition-Metal Catalyst[J]. Chinese Journal of Organic Chemistry, 2023, 43(12): 4251-4260.

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图/表 11

图1. 具有代表性的含硒生物活性分子

Figure 1. Representative selenium-containing bioactive molecules

图式1. 构建C(sp2)—Se键的方法

Scheme 1. Method of constructing C(sp2)—Se bond

Entry	Catalyst	Solvent	Oxidant	T/℃	Additive	Yield^b/%
1	Cu(OAc)₂	MeCN	K₂S₂O₈	100		56
2	FeCl₃	MeCN	K₂S₂O₈	100		79
3	Co(OAc)₂	MeCN	K₂S₂O₈	100		53
4		MeCN	K₂S₂O₈	100		78
5		MeCN	Ag₂CO₃	100		0
6		MeCN	PhI(OAc)₂	100		Trace
7		MeCN	Oxone	100		42
8		DCE	K₂S₂O₈	100		63
9		丙酮	K₂S₂O₈	100		0
10		DMSO	K₂S₂O₈	100		0
11		DMF	K₂S₂O₈	100		0
12		MeCN	K₂S₂O₈	80		Trace
13		MeCN	K₂S₂O₈	110		77
14		MeCN	K₂S₂O₈	100	KF	74
15		MeCN	K₂S₂O₈	100	Selectfluor	86
16^c		MeCN	K₂S₂O₈	100	Selectfluor	85

表1. 芳酰胺C—Se键构建反应最优条件的选择a

Table 1. Selection of optimum conditions for the construction of C—Se bond of arylamides

表2. 多种吡啶酰胺类化合物与二苯基二硒醚的反应结果a

Table 2. Results of the reaction of various pyridine amides with diphenyl diselenethers

表3. 多种苯甲酰胺类化合物与二苯基二硒醚的反应结果a

Table 3. Results of the reaction of various benzoyl amine with diphenyl diselenethers

表4. 多种(环)烷基酰胺类化合物与二苯基二硒醚的反应a

Table 4. Reaction of various (cyclic) alkyl amides with diphenyl diselenethers

图式2. 克级反应

Scheme 2. Gram grade reaction

图式3. 自由基抑制剂添加剂的设计实验

Scheme 3. Design experiment of free radical inhibitor additive

图式4. 酰胺基团必要性验证实验

Scheme 4. Validation experiment of amide group necessity

图式5. N上活泼H必要性实验

Scheme 5. Necessity experiment of active H on N

图式6. 推测的无过渡金属条件下构建C(sp2)—Se键的反应机理

Scheme 6. Inferred reaction mechanism of constructing C (sp2)—Se bond without transition metal is

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