Diastereoselective synthesis of 2-methoxyimidoyloxiranes via dimethyl phosphite-mediated coupling of α-keto N-sulfinyl imidates with aldehydes.
Dimethyl phosphite-initiated coupling of α-keto N-tert-butylsulfinyl imidates with aldehydes is reported. The epoxide formation involves a cascade transformation initiated by base-promoted addition of phosphite to α-ketoimidates, followed by [1,2]-phospha-Brook rearrangement. This generates α-phosphonyloxy enolates that are subsequently intercepted by aldehydes, leading to [1,4] O→O dialkoxyphosphinyl migration and finally to intramolecular ring closure. This protocol was used to synthesize a range of enantioenriched trans-α,β-epoxy imidates in moderate to high yields with excellent diastereoselectivities.
Key Laboratory of Plant Resources and Chemistry of Arid Zones, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi 830011, China. clu@ms.xjb.ac.cn xuyj@ms.xjb.ac.cn and University of Chinese Academy of Sciences, Beijing 100049, China.
Wei
W
Huang
Key Laboratory of Plant Resources and Chemistry of Arid Zones, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi 830011, China. clu@ms.xjb.ac.cn xuyj@ms.xjb.ac.cn.
Hui
H
Liu
Key Laboratory of Plant Resources and Chemistry of Arid Zones, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi 830011, China. clu@ms.xjb.ac.cn xuyj@ms.xjb.ac.cn.
Chong-Dao
CD
Lu
Key Laboratory of Plant Resources and Chemistry of Arid Zones, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi 830011, China. clu@ms.xjb.ac.cn xuyj@ms.xjb.ac.cn.
Yan-Jun
YJ
Xu