Transition-State Stabilization by Secondary Orbital Interactions between Fluoroalkyl Ligands and Palladium During Reductive Elimination from Palladium(aryl)(fluoroalkyl) Complexes.

ABSTRACT: Palladium-catalyzed fluoroalkylations of aryl halides are valuable reactions for the synthesis of fluorinated, biologically active molecules. Reductive elimination from an intermediate Pd(aryl) (fluoroalkyl) complex is the step that forms the C(aryl)-C(fluoroalkyl) bond, and this step typically requires higher temperatures and proceeds with slower rates than the reductive elimination of nonfluorinated alkylarenes from the analogous Pd(aryl) (alkyl) complexes. The experimental rates of this step correlate poorly with common parameters, such as the steric property or the electron-withdrawing ability of the fluoroalkyl ligand, making the prediction of rates and the rational design of Pd-catalyzed fluoroalkylations difficult. Therefore, a systematic study of the features of fluoroalkyl ligands

SUBMITTER: Kalkman ED 

PROVIDER: S-EPMC12316061 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature