三氟甲磺酸酐介导炔酰胺与吡啶加成反应的研究

doi:10.6023/cjoc202203061

摘要/Abstract

基于三氟甲磺酸酐介导炔酰胺与吡啶加成反应, 建立了含烯胺结构吡啶季铵盐的合成方法. 经过13个底物拓展验证, 采用该方法制备含烯胺结构吡啶季铵盐的收率在65%~90%之间. 该方法中吡啶氮原子高区域选择性地与炔酰胺叁键的α位进行加成, 且产物以Z构型为主(Z:E>20:1).

关键词: 炔酰胺, 吡啶, 加成反应, 吡啶季铵盐

A convenient approach to pyridine quaternary ammonium salts containing enamine fragment has been developed, which features a trifluoromethyl sulfonic anhydride mediated regioselective addition process of pyridine with ynamides. Using this method, a variety of substituted pyridine quaternary ammonium salts containing enamine fragment 3a~3m were prepared in moderate to excellent yields with high regioselectivities (Z:E up to 20:1).

Key words: ynamides, pyridine, addition reaction, pyridine quaternary ammonium salt

引用此文

宋昊儒, 孙建婷, 吕敏, 刘艺雯, 魏邦国. 三氟甲磺酸酐介导炔酰胺与吡啶加成反应的研究[J]. 有机化学, 2022, 42(8): 2433-2437.

Haoru Song, Jianting Sun, Min LÜ, Yiwen Liu, Bangguo Wei. Trifluoromethyl Sulfonic Anhydride Mediated Addition of Pyridine with Ynamides[J]. Chinese Journal of Organic Chemistry, 2022, 42(8): 2433-2437.

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图/表 6

图式1. 炔酰胺结构中三键的电性分析

Scheme 1. Electrical analysis of three bonds in ynamides

图式2. 炔酰胺与吡啶的加成反应

Scheme 2. Addition process of ynamides with pyridine

Entry	Additive (equiv.)	Time/h	Yield^b/%	Z:E^c
1	Sc(OTf)₃ (0.2)	10	NR	—
2	Er(OTf)₃ (0.2)	10	NR	—
3	TfOH (1.1)	1	Complex	—
4	Tf₂O (1.1)	1	85	>20:1
5	Tf₂O (1.1)	2	75	>20:1

表1. 炔酰胺与吡啶的反应条件优化a

Table 1. Screening of optimal conditions for the reaction of ynamides with pyridine

表2. 炔酰胺与吡啶反应底物拓展a

Table 2. Reaction substrate expansion of ynamides with pyridine

图1. 化合物3a的晶体结构

Figure 1. Crystal structure of compound 3a

图式3. 炔酰胺与吡啶加成反应机理推测

Scheme 3. Speculation on the reaction mechanism of ynamides with pyridine

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