Mechanistic Insights into Sc(III)-Catalyzed Asymmetric Homologation of Ketones with Diazo Compounds: How Trans Influence Assists in Controlling Stereochemistry.
Chemistry
; 30(21): e202303873, 2024 Apr 11.
Article
in En
| MEDLINE
| ID: mdl-38357809
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.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Chemistry
Journal subject:
QUIMICA
Year:
2024
Document type:
Article
Country of publication:
Germany