Ring walking as a regioselectivity control element in Pd-catalyzed C-N cross-coupling

Madeleine C. Deem, Joshua S. Derasp, Thomas C. Malig, Kea Legard, Curtis P. Berlinguette and Jason E. Hein ()
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Madeleine C. Deem: University of British Columbia
Joshua S. Derasp: University of British Columbia
Thomas C. Malig: University of British Columbia
Kea Legard: University of British Columbia
Curtis P. Berlinguette: University of British Columbia
Jason E. Hein: University of British Columbia

Nature Communications, 2022, vol. 13, issue 1, 1-11

Abstract: Abstract Ring walking is an important mechanistic phenomenon leveraged in many catalytic C-C bond forming reactions. However, ring walking has been scarcely studied under Buchwald-Hartwig amination conditions despite the importance of such transformations. An in-depth mechanistic study of the Buchwald-Hartwig amination is presented focussing on ligand effects on ring walking behavior. The ability of palladium catalysts to promote or inhibit ring walking is strongly influenced by the chelating nature of the ligand. In stark contrast, the resting state of the catalyst had no impact on ring walking behavior. Furthermore, the complexity of the targeted system enabled the differentiation between catalysts which undergo ring walking versus diffusion-controlled coupling. The insights gained in this study were leveraged to achieve desymmetrization of a tetrabrominated precursor. A small library of asymmetric 2,2′,7,7′-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9’spirobifluorene (SpiroOMeTAD) derivatives were successfully synthesized using this strategy highlighting the ease with which libraries of these compounds can be accessed for screening.

Date: 2022
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DOI: 10.1038/s41467-022-30255-1

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