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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

Canty, AJ and Ariafard, A ORCID: 0000-0003-2383-6380 2021 , '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, vol. 41, no. 3 , pp. 293-300 , doi: 10.1021/acs.organomet.1c00644.

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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 Type: Article
Authors/Creators:Canty, AJ and Ariafard, A
Keywords: catalysis, DFT, computation, palladium catalysis, acrylamide synthesis
Journal or Publication Title: Organometallics
Publisher: Amer Chemical Soc
ISSN: 0276-7333
DOI / ID Number: 10.1021/acs.organomet.1c00644
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Copyright © 2022 American Chemical Society

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