In the synthesis of 2,2,2-trifluoroethyl-substituted acrylamides, two-stage palladium-catalysis is indicated experimentally, including oxidative alkylation of Pd^II to Pd^IV by [I^IIIMes(CH₂CF₃)]⁺ (Besset et al., Chem. Commun., 2021, 57, 6241). For N-(quinolin-8-yl)-2-(phenyl)acrylamide [LH₂ = H₂C═C(Ph)–C(O)–NH∼N], studied by density functional theory herein, the first stage involves palladium acetate-promoted NH-deprotonation and concerted metalation-deprotonation CH-activation for Pd(OAc)₂(LH₂), followed by the transfer of [CH₂CF₃]⁺ from I^III to give a Pd^IV intermediate that undergoes reductive elimination to form the acrylamide-CH₂CF₃ linkage. The second stage employs [Pd(LH)(NCMe)]⁺ as the catalyst, with steps including outer-sphere CH-activation by triflate and crucial roles for Pd^IV, acetonitrile solvent, and N-protonation of the product by triflic acid to form [LH₂(CH₂CF₃)]⁺. In an apparently unique process, the first stage is faster than the second and produces the catalyst, but the second stage is catalytic to provide high yields of the product.

Item Type:	Refereed Article
Keywords:	catalysis, DFT, computation, palladium catalysis, acrylamide synthesis
Research Division:	Chemical Sciences
Research Group:	Inorganic chemistry
Research Field:	Transition metal chemistry
Objective Division:	Expanding Knowledge
Objective Group:	Expanding knowledge
Objective Field:	Expanding knowledge in the chemical sciences
UTAS Author:	Canty, AJ (Professor Allan Canty)
UTAS Author:	Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:	148826
Year Published:	2021
Web of Science® Times Cited:	1
Deposited By:	Chemistry
Deposited On:	2022-02-15
Last Modified:	2022-03-01
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