Transition-Metal-Free Catalytic Carboalkoxylation of Styrenes at Room Temperature.

Herein, we describe the first transition-metal-free catalytic carboalkoxylation of styrenes with aryl diazonium salts by Meerwein addition in the presence of a phenalenyl ligand at room temperature without requiring any light stimulation. This three-component reaction allows facile difunctionalization of styrene derivatives with various alcohols (such as 1, 2, and 3°) as the source of alkoxy group during this transformation. The key intermediates and the transition states involved in this reaction path were unraveled by a series of control experiments coupled with density functional theory calculations. The full mechanistic investigation provides an understanding of the selectivity toward carboalkoxylation (Meerwein arylation addition elimination) in the presence of various alcohols over the simple arylation to multiple bond (Meerwein arylation-elimination) reaction.