Stereoselective synthesis of alpha-(dichloromethyl)amines, alpha-(chloromethyl)amines, and alpha-chloroaziridines

作者：Li, Desheng; Li, Ya^*; Chen, Zhiqiu; Shang, Huaqi; Li, Hongsen; Ren, Xinfeng

来源：RSC Advances, 2014, 4(27): 14254-14263.

DOI：10.1039/c4ra00471j

• HALOGENATED IMINO COMPOUNDS
• CHIRAL N-ACYLHYDRAZONES
• ASYMMETRIC-SYNTHESIS
• RADICAL-ADDITION
• FACILE SYNTHESIS
• FUNCTIONALIZED AZIRIDINES
• STEREOSPECIFIC SYNTHESIS
• ACID-CHLORIDES
• REDUCTION
• REARRANGEMENT

Protocols for the stereoselective synthesis of alpha-(dichloromethyl)amines, alpha-(chloromethyl)amines, and alpha-chloroaziridines are presented. Diastereoselective synthesis of alpha-(dichloromethyl)amines was achieved based on nucleophilic dichloromethylation of aromatic N-tert-butylsulfinyl aldimines with (dichloromethyl)trimethylsilane at a low reaction temperature. Slowly warming the reaction mixture up to room temperature gave alpha-chloro cis-aziridines. Additionally, with Bu3SnH as the reductant, alpha-(dichloromethyl)amines were readily obtained from easily accessible alpha-(trichloromethyl)amines via mono-dechlorination. Over-reduction was successfully suppressed. Subsequent radical mono-dechlorination of the alpha-(dichloromethyl)amines gave the corresponding alpha-(chloromethyl)amines in good to excellent yields.

• 出版日期2014
• 单位上海工程技术大学