The polyhalomethane based superelectrophilic systems allowed us to accomplish the first efficient and selective carbonylation of n-butane and n-pentane with CO. Depending on the nature of the superelectrophilic system, Me3CCOOR or EtCH (Me) COOR (R= H, Alk) can be obtained at− 20° C, 1 atm from n-butane and CO after water (or alcohol) treatment in≈ 90% yield based on the superelectrophilic system. Pentane reacts with CO in the presence of ...