Carbanion Stabilization by Distal Silyloxy Groups. Origin of the High Diastereoselectivity in the Formation of Quaternary Centers with Aryllead(IV) Triacetate Reagents
- Resource Type
- Authors
- Philip J. Wenzel; Gregory I. Elliott; Jinzhen Lin; Brian S. Gerstenberger; Joseph P. Konopelski; Hongbo Deng
- Source
- Organic Letters. 4:4121-4124
- Subject
- Silylation
Stereochemistry
Chemistry
Ab initio quantum chemistry methods
Yield (chemistry)
Reagent
Organic Chemistry
Physical and Theoretical Chemistry
Biochemistry
Medicinal chemistry
Carbanion
- Language
- ISSN
- 1523-7052
1523-7060
Derivatives of methyl 5-hydroxy-2-oxo-1-cyclohexanecarboxylate react with aryllead(IV) reagents in high yield and with wide variation in diastereoselectivity. Ab initio calculations are consistent with a heretofore unrecognized attraction between the carbanionic center of the β-ketoester intermediate and the distal OSiR3 group. This attractive interaction stabilizes the silyl group in the axial conformation and leads to the excellent trans diastereoselection in the formation of quaternary centers.