Transition‐Metal Free Dialkylation to Construct All‐Carbon Quaternary Centers From Alkyl Chlorides and 1,3‐Dicarbonyl Compounds

ABSTRACT A practical and efficient potassium trimethylsilanolate/nitrile system for constructing all‐carbon quaternary centers has been developed. This transition‐metal free protocol utilizes readily available chlorides and 1,3‐dicarbonyl compounds, enabling the selective formation of two C─C bonds in a single operation. The reaction features broad substrate scope, good functional group tolerance, large scale synthesis, and further structural modification, providing a mild approach to access quaternary centers in moderate to excellent yields.