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. 2010 Oct 13;132(40):14073-5.
doi: 10.1021/ja1073799.

A new palladium precatalyst allows for the fast Suzuki-Miyaura coupling reactions of unstable polyfluorophenyl and 2-heteroaryl boronic acids

Tom Kinzel  1 , Yong Zhang, Stephen L Buchwald
Affiliations

A new palladium precatalyst allows for the fast Suzuki-Miyaura coupling reactions of unstable polyfluorophenyl and 2-heteroaryl boronic acids

Tom Kinzel et al. J Am Chem Soc. .

Abstract

Boronic acids which quickly deboronate under basic conditions, such as polyfluorophenylboronic acid and five-membered 2-heteroaromatic boronic acids, are especially challenging coupling partners for Suzuki-Miyaura reactions. Nevertheless, being able to use these substrates is highly desirable for a number of applications. Having found that monodentate biarylphosphine ligands can promote these coupling processes, we developed a precatalyst that forms the catalytically active species under conditions where boronic acid decomposition is slow. With this precatalyst, Suzuki-Miyaura reactions of a wide range of (hetero)aryl chlorides, bromides, and triflates with polyfluorophenyl, 2-furan, 2-thiophene, and 2-pyrroleboronic acids and their analogues proceed at room temperature or 40 °C in short reaction times to give the desired products in excellent yields.

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Figures

Scheme 1
Scheme 1
Initial observation of the coupling of 1 with a stoichiometric amount of an oxidative-addition complex 9.
Scheme 2
Scheme 2
Synthesis of precatalyst 13.
Chart 1
Chart 1
Boronic acids that easily undergo protodeboronation in aqueous base to give the parent arene.
Chart 2
Chart 2
XPhos-containing precatalysts used in this study.
See this image and copyright information in PMC

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