α-氰醇甲磺酸酯在合成α-氨基腈类化合物中的应用

doi:10.6023/cjoc202308015

摘要/Abstract

报道了无过渡金属存在下α-氰醇甲磺酸酯与芳香胺的亲核取代反应. 该方法的原料简单易得, 反应条件温和, 具有良好的底物适用性和官能团兼容性, 以较好的产率得到了一系列重要的α-氨基腈类化合物. 更重要的是, 该方法还适用于含季碳中心的α-氰醇甲磺酸酯以及其它氮亲核试剂, 得到的α-氨基腈非常容易衍生化.

关键词: α-氨基腈, α-氰醇甲磺酸酯, 芳香胺, 亲核取代

An efficient synthesis of α-aminonitriles via nucleophilic substitution of α-cyanohydrin methanesulfonates with aromatic amines was developed. This transition metal-free protocol has the advantages of cheap and easily available starting materials, broad substrate scope, excellent functional group compatibility, and very mild and simple operations. Furthermore, this strategy could also be applicable to quaternary α-cyanohydrin methanesulfonates and various nitrogen nucleophiles. A range of derivatives were readily obtained through subsequent elaboration of α-aminonitriles.

Key words: α-aminonitrle, α-cyanohydrin methanesulfonate, aromatic amine, nucleophilic substitution

引用此文

张勇, 田志高, 黄琳, 侯秋飞, 范红红, 汪万强. α-氰醇甲磺酸酯在合成α-氨基腈类化合物中的应用[J]. 有机化学, 2024, 44(2): 561-572.

Yong Zhang, Zhigao Tian, Lin Huang, Qiufei Hou, Honghong Fan, Wanqiang Wang. Application of α-Cyanohydrin Methanesulfonates for the Synthesis of α-Aminonitriles[J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 561-572.

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图/表 7

图1. 具有生物活性的α-氨基腈类化合物

Figure 1. Representative biologically important α-aminonitriles

图式1. α-氨基腈类化合物的合成方法

Scheme 1. Strategies for the construction of α-aminonitriles

Entry	Base	Solvent	Yield^b/%
1	LiOH	CH₃CN	23
2	LiOH	Acetone	41
3	LiOH	EtOAc	55
4	LiOH	i-PrOH	69
5	LiOH	Toluene	73
6	CsOAc	Toluene	30
7	NaHCO₃	Toluene	54
8	K₂CO₃	Toluene	84
9	NaOH	Toluene	30
10	LiOt-Bu	Toluene	23
11	—	Toluene	70

表1. 优化反应条件a

Table 1. Optimization of reaction conditions

表2. 芳香胺的底物范围a

Table 2. Scope of anilines

表3. α-氰醇甲磺酸酯的底物范a

Table 3. Scope of α-cyanohydrin methanesulfonates

图式2. 氮亲核试剂与α-氰醇甲磺酸酯的反应

Scheme 2. Reaction between nitrogen nucleophiles and α-cya- nohydrin methanesulfonates

图式3. 产物衍生化

Scheme 3. Synthetic application

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