Aluminium-Catalyzed Selective Hydroboration of Esters and Epoxides to Alcohols: C-O Bond Activation

In this work, the molecular aluminium dihydride complex bearing an N, N'-chelated conjugated bis-guanidinate (CBG) ligand is used as a catalyst for reducing a wide range of aryl and alkyl esters with good tolerance of alkene (C=C), alkyne (C equivalent to C), halides (Cl, Br, I and F), nitrile (C equivalent to N), and nitro (NO2) functionalities. Further, we investigated the catalytic application of aluminium dihydride in the C-O bond cleavage of alkyl and aryl epoxides into corresponding branched Markovnikov ring-opening products. In addition, the chemoselective intermolecular reduction of esters over other reducible functional groups, such as amides and alkenes, has been established. Intermediates are isolated and characterized by NMR and HRMS studies, which confirm the probable catalytic cycles for the hydroboration of esters and epoxides.