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.

Published

Journal Article

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.

Full Text

Duke Authors

Cited Authors

  • Daniel, PE; Onyeagusi, CI; Ribeiro, AA; Li, K; Malcolmson, SJ

Published Date

  • January 2019

Published In

Volume / Issue

  • 9 / 1

Start / End Page

  • 205 - 210

PubMed ID

  • 31105988

Pubmed Central ID

  • 31105988

Electronic International Standard Serial Number (EISSN)

  • 2155-5435

International Standard Serial Number (ISSN)

  • 2155-5435

Digital Object Identifier (DOI)

  • 10.1021/acscatal.8b03999

Language

  • eng