We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Mechanistic Insights into Sc(III)‐Catalyzed Asymmetric Homologation of Ketones with Diazo Compounds: How Trans Influence Assists in Controlling Stereochemistry.
- Authors
Huang, Meirong; Wu, Yun‐Dong; Zhang, Xinhao
- Abstract
Asymmetric one‐carbon homologation or ring expansion of ketones with formal insertion of carbene intermediate, is a challenging but useful strategy to construct a complex skeleton. Sc(III) and chiral ligands have been employed in this regard. However, due to flexible conformations and a variety of stereo models, the origin of stereochemistry remains ambiguous. Density functional theory (DFT) calculations were carried out to explore the interactions that control the stereoselectivity of a Sc(III)‐catalyzed asymmetric homologation. The trans influence of counterions was found to affect the coordination mode of ketone to Sc(III), and consequently affect the stereoselectivity.
- Subjects
STEREOCHEMISTRY; KETONES; DENSITY functional theory; DIAZO compounds; STEREOSELECTIVE reactions
- Publication
Chemistry - A European Journal, 2024, Vol 30, Issue 21, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202303873