Related Experiment Video
Updated: Jan 2, 2026

Preparation of Enantiopure Non-Activated Aziridines and Synthesis of Biemamide B, D, and epiallo-Isomuscarine
Published on: June 13, 2022
Z-Enolate Geometry in the Thioamide Aldol Reaction Illuminated by the 7-Azaindoline Auxiliary
Roman Pluta1, Zhao Li1, Naoya Kumagai1
1Institute of Microbial Chemistry , 3-14-23 Kamiosaki , Shinagawa-ku , Tokyo 141-0021 , Japan.
Abstract:
Z or E enolate geometry is the primary determinant of diastereoselectivity in the aldol reaction. Although amide and thioamide enolates are anticipated to have predominantly the E geometry because of the intrinsic steric demand, spectroscopic confirmation of the geometry in solution has remained elusive, particularly in the realm of highly stereoselective catalytic asymmetric aldol reactions. Herein we demonstrate that the 7-azaindoline auxiliary enables direct observation of the exclusive formation of the Z-enolate of the thioamide en route to a highly syn-selective aldol reaction.
Related Concept Videos
Dehydration of Aldols to Enals: Base-Catalyzed Aldol Condensation
α-Alkylation of Ketones via Enolate Ions
Enolate Mechanism Conventions
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
Crossed Aldol Reaction Using Strong Bases: Directed Aldol Reaction
Base-Catalyzed Aldol Addition Reaction

![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)