A new protocol for synthesizing diarylmethanes using a benzyltitanium reagent as a nucleophile

Abstract

The first palladium-catalyzed cross-coupling of various substituted benzyltitaniums with aryl triflates is presented for the synthesis of diarylmethanes in yields of up to 94% through highly selective C–O bond functionalization. The benzyltitaniums act as nucleophiles to realize the C(sp2)–C(sp3) cross-coupling with high efficiency in short reaction times. The reactions proceed at 60°C and show excellent functional groups tolerance.

Recent advances in the application of ligands in palladium-catalyzed chemoselective coupling reactions at C–Br, C–OTf, and C–Cl sites

“…The selectivity at triflates would be highly dominated by this type of catalytic system and entirely independent of the applied solvent, temperature, and nucleophiles. 62–80…”

“…The selectivity at triflates would be highly dominated by this type of catalytic system and entirely independent of the applied solvent, temperature, and nucleophiles. [62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79][80] Chemoselectivity in cross-coupling between aryl bromides and aryl triflates using Buchwald-type phosphines is rarely reported in the literature. Chang 62 and Jana 67 published two examples that applied Pd/L7 (SPhos) and Pd/L12 (DavePhos) Buchwald-type phosphine catalytic systems to achieve O-triflylselective carbonylative arylation and carboxylation, respectively.…”