Z-Enolate Geometry in the Thioamide Aldol Reaction Illuminated by the 7-Azaindoline Auxiliary
| Autor: | Naoya Kumagai, Zhao Li, Roman Pluta, Masakatsu Shibasaki |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Steric effects 010405 organic chemistry Organic Chemistry Direct observation Geometry 010402 general chemistry 01 natural sciences Biochemistry 0104 chemical sciences Catalysis chemistry.chemical_compound chemistry Aldol reaction Amide Stereoselectivity Physical and Theoretical Chemistry Thioamide |
| Zdroj: | Organic Letters. 22:791-794 |
| ISSN: | 1523-7052 1523-7060 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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