Silver catalysis in organic synthesis: A computational view

In the past decade, silver catalysis has emerged as a highly enabling tool in organic chemistry, and calculations can play a critical role in elucidating the mechanism by which silver-catalyzed reactions proceed. This review will summarize progress in density functional theory (DFT) studies on several kinds of silver-catalyzed organic reactions, including cycloaddition, CO2 absorption and decarboxylation, fluorination, asymmetric synthesis in cyclization reaction, hydrogenation, and carbene/nitrene/silylene transfer. The review covers activation and coordination modes for various silver complexes, highlighting σ-activation, π-activation or silver carbene/nitrene/silylene generation. We summarize the most common reaction pathways, and explain solvent, ligand and substituent effects on catalytic activity and selectivity.