Kinetic Resolution of Tertiary 2‐Alkoxycarboxamido‐Substituted Allylic Alcohols by Chiral Phosphoric Acid Catalyzed Intramolecular Transesterification

Abstract

Ah ighly enantioselective kinetic resolution of tertiary 2-alkoxycarboxamido allylic alcohols has been achieved through ac hiral phosphoric acid catalyzed intramolecular transesterification reaction. Both alkyl,aryl-and dialkylsubstituted tertiary allylic alcohols were resolved with excellent efficiencies,affording both the recovered tertiary alcohols and the carbamate products with high enantioselectivities (with sf actors up to 164.6). Ag ram-scale reaction with 1mol % catalyst loading and the facile conversion of the enantioenriched products into useful chiral building blocks,s uch as chiral oxazolidinones and b-amino alcohols,d emonstrate the value of this reaction.

Kinetic Resolution of Sulfoximines via Asymmetric Organocatalyzed Formation of Benzothiadiazine-1-oxides

“…7a,8,15 However, to the best of our knowledge, the KR of racemic sulfoximines bearing two different aryl groups has been scarcely documented. 16 With our continuous interest in developing novel KR methods for alcohols and amines, 17 herein we present the KR of racemic sulfoximines bearing both S,S-diaryl-and aryl,alkyl-disubstitutions, through the CPA-catalyzed dehydrative cyclization reaction. Notably, this approach enables the direct synthesis of chiral benzothiadiazine-1-oxide, a type of cyclic sulfoximines of significance importance in medicinal chemistry, especially those inaccessible by the previous TM-catalyzed desymmetrization methods (Figure 1d)…”