With the vast array of options and numerous catalyst examples currently available for cross-coupling applications, only truly substantial development advances are likely to get noticed, nowadays. Fortunately, our group has been able to uncover impactful and evolutionary ligand design elements that are able to elevate catalyst performance levels above those of modern phosphine-based palladium systems. Herein, the development of a novel meta-terarylphosphine ligand architecture – coined Cy*Phine – will be described along with its employment in palladium-mediated cross-coupling applications. Recent publications of the Pd-Cy*Phine catalyst used in copper-free Sonogashira,[1] the Mizoroki-Heck[2] and Buchwald-Hartwig amination reactions will be highlighted and a broad-based catalyst outperformance will be demonstrated relative to the state-of-the-art commercial alternatives. The source of the enhancement in catalytic efficiency will be proposed and potential opportunities to further develop this promising ligand platform will be suggested. [1] Yang, Y.; Chew, X.; Johannes, C. W.; Robins, E. G.; Jong, H.; Lim Y. H. Eur. J. Org. Chem. 2014, 7184. [2] Tay, D. W.; Jong, H.; Lim, Y.H.; Wu, W.; Chew, X.; Robins, E. G.; Johannes, C. W. J. Org. Chem. 2015, ASAP. DOI: 10.1021/acs.joc.5b00386.

Phosphine ligand evolution: Design, application, and opportunities in palladium-catalyzed cross-coupling reactions

250th National Meeting (2015)

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