Fast Addition of s‐Block Organometallic Reagents to CO₂‐Derived Cyclic Carbonates at Room Temperature, Under Air, and in 2‐Methyltetrahydrofuran

Abstract Fast addition of highly polar organometallic reagents (RMgX/RLi) to cyclic carbonates (derived from CO 2 as a sustainable C1 synthon) has been studied in 2‐methyltetrahydrofuran as a green reaction medium or in the absence of external volatile organic solvents, at room temperature, and in the presence of air/moisture. These reaction conditions are generally forbidden with these highly reactive main‐group organometallic compounds. The correct stoichiometry and nature of the polar organometallic alkylating or arylating reagent allows straightforward synthesis of: highly substituted tertiary alcohols, β ‐hydroxy esters, or symmetric ketones, working always under air and at room temperature. Finally, an unprecedented one‐pot/two‐step hybrid protocol is developed through combination of an Al‐catalyzed cycloaddition of CO 2 and propylene oxide with the concomitant fast addition of RLi reagents to the in situ and transiently formed cyclic carbonate, thus allowing indirect conversion of CO 2 into the desired highly substituted tertiary alcohols without need for isolation or purification of any reaction intermediates.