Switchable Site‐Selective Catalytic Carboxylation of Allylic Alcohols with CO2

A switchable site‐selective catalytic carboxylation of allylic alcohols has been developed in which CO2 is used with dual roles, both facilitating C−OH cleavage and as a C1 source. This protocol is characterized by its mild reaction conditions, absence of stoichiometric amounts of organometallic reagents, broad scope, and exquisite regiodivergency which can be modulated by the type of ligand employed. Double agent: In the title reaction, CO2 serves as both a facilitator for the C−OH cleavage and as a C1 source. This reaction is the first example of a cross‐electrophile coupling of unprotected alcohols in the absence of stoichiometric amounts of organometallic species. The procedure has broad scope and an exquisite regiodivergency which can be modulated by the ligand‐type employed.