A synthesis of the hasubanan alkaloids hasubanonine, runanine, and aknadinine via a unified route was attempted. Construction of key phenanthrene intermediates by a Suzuki coupling-Wittig olefination-ring-closing metathesis sequence allowed a convergent and flexible approach. Conversion of the phenanthrenes into the target structures was projected to involve six steps including phenolic oxidation, ketone allylation, anionic oxy-Cope rearrangement, and acid-promoted cyclization. The final step was thwarted by a pinacol-like rearrangement that delivered the unnatural isohasubanan alkaloid skeleton. The structures of the products were established by exhaustive NMR experiments and confirmed by GIAO (13)C NMR calculations of runanine, isorunanine, and three other isomers. These computations revealed some inconsistencies with the benzene solvent correction which suggest that caution should be used in employing this algorithm. The racemic synthesis of isohasubanonine was transformed into an enantioselective synthesis by the discovery that Nakamura's chiral bisoxazoline-ligated allylzinc reagent mediates the enantioselective allylation of ketone 19 in 93% ee. This method could be extended to three other structurally related ketones (92-96% ee), and the enantioselective syntheses of two other isohasubanan alkaloids, isorunanine and isoaknadinine, were accomplished. Racemic isohasubanonine was found to be an ineffective analgesic agent.

ABSTRACT1 Encouraging sustainable living by raising awareness of resource consumption has long been a topic within HCI. However, getting people to change behavior when it comes to energy consumption is difficult. This is one of the major challenges ahead for future energy systems, in particular if resources are renewable and plentiful. We developed the ClockCast prototypes (web and clock forecast) to explore demand response and the flexibility potential of everyday practices. We wanted to reframe the conversation on demand response: from highlighting when not to use energy to highlighting when to use it. The ClockCast prototypes display the best times to use electricity, and they were complemented by proactive and positive suggestions. We conducted a pilot study with five different households to uncover the socio-technical challenges around shifting consumption and the participants' experiences with the prototypes. While the participants increased their awareness of the environmental implications of their actions, shifted some electricity use, and found the forecasts useful, some participants also reported newfound guilt when they did not follow the forecasts.

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