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Open AccessFeature PaperCommunication
Molecules 2018, 23(12), 3134; https://doi.org/10.3390/molecules23123134

Pd-Catalyzed Suzuki-Miyaura Cross-Coupling of Pentafluorophenyl Esters

Department of Chemistry, Rutgers University, 73 Warren Street, Newark, NJ 07102, USA
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Received: 12 October 2018 / Revised: 15 November 2018 / Accepted: 23 November 2018 / Published: 29 November 2018
(This article belongs to the Special Issue Amide Bond Activation)
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Abstract

Although the palladium-catalyzed Suzuki-Miyaura cross-coupling of aryl esters has received significant attention, there is a lack of methods that utilize cheap and readily accessible Pd-phosphane catalysts, and can be routinely carried out with high cross-coupling selectivity. Herein, we report the first general method for the cross-coupling of pentafluorophenyl esters (pentafluorophenyl = pfp) by selective C–O acyl cleavage. The reaction proceeds efficiently using Pd(0)/phosphane catalyst systems. The unique characteristics of pentafluorophenyl esters are reflected in the fully selective cross-coupling vs. phenolic esters. Of broad synthetic interest, this report establishes pentafluorophenyl esters as new, highly reactive, bench-stable, economical, ester-based, electrophilic acylative reagents via acyl-metal intermediates. Mechanistic studies strongly support a unified reactivity scale of acyl electrophiles by C(O)–X (X = N, O) activation. The reactivity of pfp esters can be correlated with barriers to isomerization around the C(acyl)–O bond. View Full-Text
Keywords: Suzuki-Miyaura; cross-coupling; aryl esters; C–O activation; Pd-catalysis Suzuki-Miyaura; cross-coupling; aryl esters; C–O activation; Pd-catalysis
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).

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Buchspies, J.; J. Pyle, D.; He, H.; Szostak, M. Pd-Catalyzed Suzuki-Miyaura Cross-Coupling of Pentafluorophenyl Esters. Molecules 2018, 23, 3134.

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