Palladium-Catalyzed Synthesis of α
-Trifluoromethyl Benzylic Amines via Fluoroarylation of gem
-Difluoro-2-azadienes Enabled by Phosphine-Catalyzed Formation of an Azaallyl-Silver Intermediate.
We report the synthesis of α
-trifluoromethyl benzylic amines through the vicinal fluoroarylation of gem-
difluoro-2-azadienes. Our studies indicate that XPhos plays an important role as a phase transfer catalyst that promotes the addition of AgF to the difluoroazadiene, generating an α-
trifluoromethyl azaallyl-silver intermediate that we have characterized by NMR spectroscopy. This intermediate likely transmetallates to Pd, coupling several aryl iodides to deliver products in up to 90% yield. Modification of the azadiene's activating group facilitates challenging cross-couplings.
Daniel, PE; Onyeagusi, CI; Ribeiro, AA; Li, K; Malcolmson, SJ
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