Guerbet-type β-alkylation of secondary alcohols catalyzed by chromium chloride and its corresponding NNN pincer complex

β-Alkylation of alcohols has been efficiently accomplished using readily available 3d metal Cr under microwave conditions in air. Well-defined molecular Cr is involved with a KIE of 7.33 and insertion of α-alkylated ketone into Cr–H bond as the RDS.