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Two-stage catalysis in the Pd-catalyzed formation of 2,2,2-trifluoroethyl-substituted acrylamides: oxidative alkylation of PdII by an IIII reagent and roles for acetate, triflate, and triflic acid

Citation

Canty, AJ and Ariafard, A, Two-stage catalysis in the Pd-catalyzed formation of 2,2,2-trifluoroethyl-substituted acrylamides: oxidative alkylation of PdII by an IIII reagent and roles for acetate, triflate, and triflic acid, Organometallics, 41, (3) pp. 293-300. ISSN 0276-7333 (2021) [Refereed Article]

Copyright Statement

Copyright 2022 American Chemical Society

DOI: doi:10.1021/acs.organomet.1c00644

Abstract

In the synthesis of 2,2,2-trifluoroethyl-substituted acrylamides, two-stage palladium-catalysis is indicated experimentally, including oxidative alkylation of PdII to PdIV by [IIIIMes(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 IIII to give a PdIV 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 PdIV, 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 Details

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
Downloads:0

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