Expedient Synthesis of Functionalized Triarylmethanols through Tandem Formation of Geminal C-C and C-O Bonds

The rearrangement/oxidation of N,N-disubstituted anilines and the formal dehydrogenative cross-coupling of diarylmethanols with aniline derivatives have been developed for the preparation of symmetric and unsymmetric functionalized triarylmethanols. Both reactions proceed smoothly in trifluoroacetic acid in the presence of an inexpensive oxidant (manganese dioxide or potassium persulfate) and a catalytic amount of palladium diacetate to give a range of functionalized triarylmethanols in moderate to good yields and with extremely high regioselectivity. The two unprecedented reactions involve tandem formation of geminal C?C and C?O bonds, and they are synthetically useful, atom-efficient, and operationally simple.