Mechanistically informed selection rules for competing β-hydride and β-heteroatom eliminations

Alkylpalladium complexes are important intermediates in several industrially relevant catalytic reactions, such as the Mizoroki–Heck reaction, alkyl C–H activation and ethylene polymerization. β-elimination—of either a hydride (β-Η) or heteroatom (β-Χ)—is most common decomposition pathway for these intermediates; this can lead to desired it hinder reaction progress, and/or vinyl halide co-polymerizations. Despite importance of elimination processes, little mechanistic understanding exists with respect factors that control them. Here we present systematic investigation govern competition between β-Η β-Χ catalytically alkylpalladium complexes. These results enabled us derive selection rules dictate ligand choice selectivity elimination. This knowledge may allow chemists manipulate β-eliminations design chemoselective reactions wide range applications. β-hydride β-heteroatom eliminations elementary steps many used synthesis drug molecules polymers. However, processes often compete leading unpredictable outcomes. Here, series mechanistically informed developed selectively achieve