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-trifluoromethy...

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Bibliographic Details
Published in:ACS catalysis 2019-01, Vol.9 (1), p.205-210
Main Authors: Daniel, Paige E, Onyeagusi, Chibueze I, Ribeiro, Anthony A, Li, Kangnan, Malcolmson, Steven J
Format: Article
Language:English
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Summary: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.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.8b03999