Reactivity

  • 82. Effect of solvent on radical cyclisation pathways: SRN 1 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.

    Organic & Biomolecular Chemistry 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.

  • 78. KOtBu: A Privileged Reagent for Electron Transfer Reactions?

    Many recent studies have used KOtBu in organic reactions that involve single electron transfer; in the literature, the electron transfer is proposed to occur either directly from the metal alkoxide or indirectly, following reaction of the alkoxide with a solvent or additive. These reaction classes include coupling reactions of halobenzenes and arenes, reductive cleavages of […]

    Barham, J. P.; Coulthard, G.; Emery, K. J.; Doni, E.; Cumine, F.; Nocera, G.; John, M. P.; Berlouis, L. E. A.; McGuire, T.; Tuttle, T.; Murphy, J. A.

    J. Am. Chem. Soc. 2016 138 7402.

  • 75. Enzymatically activated emulsions stabilised by interfacial nanofibre networks

    We report on-demand formation of emulsions stabilised by interfacial nanoscale networks. These are formed through biocatalytic dephosphorylation and self-assembly of Fmoc(9-fluorenylmethoxycarbonyl)dipeptide amphiphiles in aqueous/organic mixtures. This is achieved by using alkaline phosphatase which transforms surfactant-like phosphorylated precursors into self-assembling aromatic peptide amphiphiles (Fmoc-tyrosine-leucine, Fmoc-YL) that form nanofibrous networks. In biphasic organic/aqueous systems, these networks form […]

    Inês P. Moreira; Ivan Ramos Sasselli; Daniel A. Cannon; Meghan Hughes; Dimitrios A. Lamprou; Tell Tuttle; Rein V. Ulijn

    Soft Matter 2016 12 2623.