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

• Published in: Angewandte Chemie International Edition Vol. 58; no. 30; pp. 10315 - 10319
• Main Authors: Rajkumar, Subramani, He, Shunlong, Yang, Xiaoyu
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 22-07-2019
• Edition: International ed. in English
• Subjects: Alcohol; Alcohols; Aromatic compounds; carbamates; Chemical industry; chiral Brønsted acids; Enantiomers; kinetic resolution; organocatalysis; Oxazolidinones; Phosphoric acid; Substitutes; Transesterification; organocatalysis; kinetic resolution; alcohols; carbamates; chiral Brønsted acids
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201905034

A highly enantioselective kinetic resolution of tertiary 2‐alkoxycarboxamido allylic alcohols has been achieved through a chiral phosphoric acid catalyzed intramolecular transesterification reaction. Both alkyl,aryl‐ and dialkyl‐substituted tertiary allylic alcohols were resolved with excellent efficiencies, affording both the recovered tertiary alcohols and the carbamate products with high enantioselectivities (with s factors up to 164.6). A gram‐scale reaction with 1 mol % catalyst loading and the facile conversion of the enantioenriched products into useful chiral building blocks, such as chiral oxazolidinones and β‐amino alcohols, demonstrate the value of this reaction.
The kinetic resolution of tertiary 2‐alkoxycarboxamido‐substituted allylic alcohols was achieved through a chiral phosphoric acid catalyzed intramolecular transesterification reaction. Both alkyl,aryl‐ and dialkyl‐substituted tertiary allylic alcohols were resolved with excellent efficiencies, with s factors up to 164.6. This method provides expedient access to enantioenriched oxazolidinones and β‐amino alcohols.