Application of α-Cyanohydrin Methanesulfonates for the Synthesis of α-Aminonitriles

doi:10.6023/cjoc202308015

Abstract

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

Cite this article

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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Fig. & Tab. 7

Figure 1. Representative biologically important α-aminonitriles

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

Table 1. Optimization of reaction conditions

Table 2. Scope of anilines

Table 3. Scope of α-cyanohydrin methanesulfonates

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

Scheme 3. Synthetic application

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