Publications [#340753] of Steven Malcolmson

Journal Articles

  1. Daniel, PE; Onyeagusi, CI; Ribeiro, AA; Li, K; Malcolmson, SJ, "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.", Acs CatalysisJanuary,, 2019, 9(1), 205-210, American Chemical Society (ACS) [doi].
    (last updated on 2021/12/07)

    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.