Diastereoselective synthesis of 2-methoxyimidoyloxiranes via dimethyl phosphite-mediated coupling of α-keto N-sulfinyl imidates with aldehydes. Issue 93 (3rd November 2016)

• Record Type: Journal Article
• Authors: Huang, Wei; Liu, Hui; Lu, Chong-Dao; Xu, Yan-Jun
• Is Part Of: Chemical communications. Volume 52:Issue 93(2016)
• Page Start: 13592
• Page End: 13595
• Publication Date: 2016-11-03
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c6cc07723d
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : A dimethyl phosphite-triggered coupling of α-keto N-tert -butylsulfinyl imidates with aldehydes provides access to enantioenriched 2-methoxyimidoyloxiranes with excellent diastereoselectivities. Abstract : 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.