Studies of 2,1-benzothiazine, silver-catalyzed rearrangement and 1,5-hydride shift

Abstract

[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT REQUEST OF AUTHOR.] Dimethyl sulfoximine was used to synthesize benzothiazines by coupling reaction. When the substrate is dibromodibenzaldehyde, water was added to complete the reaction in meso product. Also some of the 2,1-benzothiazine's derivatives were synthesized. A novel method for the rearrangement from propargylic sulfinates to allenic sulfones by silver catalysis was discovered. This reaction works under very mild conditions with quantitative yield in fast mode. Also it's scalable. By silver catalysis, the synthesis oxazolines from Nproparglamides was also discovered. This reaction was very fast, robust and in high yield. Dichlorocyclopentanone derivative reacted with alkenes to obtain 1,5-hydride shift product. It shows oxyallylic cations and alkene can react with each other in the ene-like hydride shift reaction. This result was supported by computational analysis.