Reactivity

  • 87. Iridium-Catalyzed Formyl-Selective Deuteration of Aldehydes

    We report the first direct catalytic method for formyl-selective deuterium labeling of aromatic aldehydes under mild conditions, using an iridium-based catalyst designed to favor formyl over aromatic C−H activation. A good range of aromatic aldehydes is selectively labeled, and a one-pot labeling/olefination method is also described. Computational studies support kinetic product control over competing aromatic […]

    Kerr, W. J.; Reid, M.; Tuttle, T.

    Angew. Chem. Int. Ed. 2017 56 7808.

  • 84. A study of diketopiperazines as electron-donor initiators in transition metal-free haloarene–arene coupling.

    The electron-donating ability of enolates of N,N′-disubstituted diketopiperazines is strongly influenced by the nature of the substituents.

    Cumine, F.; Zhou, S.; Tuttle, T.; Murphy, J. A.

    Org. Biomol. Chem. 2017 15 3324.

  • 82. Effect of solvent on radical cyclisation pathways: SRN1 vs. aryl–aryl bond forming mechanisms

    A recent paper identified a series of alternative cyclisation pathways of aryl radicals that resulted from electron transfer to various tethered haloarene–acetylarene substrates, in either benzene or DMSO as solvent. The electron transfer occurred from one of two enolates that were formed in the presence of KOtBu: either the enolate of the acetylarene, within the […]

    Emery, K. J.; Murphy, J. A.; Tuttle, T.

    Org. Biomol. Chem. 2017 15 920.

  • 81. C–C bond-forming reactions of ground-state aryl halides under reductive activation

    Under basic conditions aryl halides can undergo SRN1 reactions, BHAS reactions and benzyne formations. Appropriate complex substrates afford an opportunity to study inherent selectivities. SRN1 reactions are usually favoured under photoactivated conditions, but this paper reports their success using ground-state and transition metal-free conditions. In benzene, the enolate salt 12, derived by deprotonation of diketopiperazine 11, behaves […]

    Emery, K. J.; Tuttle, T.; Kennedy, A. R.; Murphy, J. A.

    Tetrahedron 2016 72 7875.