Abstract
The chemoselective reduction of amides in the presence of other more reactive reducible functional groups is a highly challenging transformation, and successful examples thereof are most valuable in synthetic organic chemistry. Only a limited number of systems have demonstrated the chemoselective reduction of amides over ketones. Until now, the aldehyde functionality has not been shown to be compatible in any catalytic reduction protocol. Described herein is a [Mo(CO)6]‐catalyzed protocol with an unprecedented chemoselectivity and allows for the reduction of amides in the presence of aldehydes and imines. Furthermore, the system proved to be tunable by variation of the temperature, which enabled for either C−O or C−N bond cleavage that ultimately led to the isolation of both amines and aldehydes, respectively, in high chemical yields.
The choice is yours: [Mo(CO)6] is demonstrated to be an efficient catalyst for the chemoselective reduction of tertiary amides in the presence of a large number of reducible groups, including imines and aldehydes. The reaction is tunable by variation of the temperature, and either an amine or an aldehyde can be obtained as the major product from the corresponding amide. TMDS=1,1,3,3‐tetramethyldisiloxane.