Synthesis and Configuration of O-Acetyl Microgrewiapine A: Phantomization of O-Acetyl 6-epi-Microgrewiapine A.

The formation of O-acetyl microgrewiapine A is investigated. NMR data for the authentic sample derived from the natural product are corrected. Wholly synthetic samples, produced from reductive N-methylation of synthetic microcosamine A (to give synthetic microgrewiapine A) followed by O-acetylation, exhibit NMR data that are identical to those of the authentic sample. The previous report that this two-step transformation proceeds with epimerization at C-6 is thus shown to be in error: the purported sample of O-acetyl 6-epi-microgrewiapine A is structurally misassigned and is, in fact, O-acetyl microgrewiapine A. A plausible rationale for the structural misassignment is advanced.

Microgrewiapine C: Asymmetric Synthesis, Spectroscopic Data, and Configuration Assignment.

The first asymmetric synthesis of microgrewiapine C, a piperidine alkaloid isolated from Microcos paniculata, is reported. This synthesis prompted correction of the 1H and 13C NMR data for the natural sample of the alkaloid, which was achieved by reanalysis of the original spectra. The corrected data for the natural product were found to be identical to those of the synthetic sample prepared herein, thus confirming the structural and relative configurational assignment of microgrewiapine C. Although comparison of specific rotation values indicates that the (1R,2S,3S,6S) absolute configuration should be assigned to the alkaloid, consideration of potential common biosynthetic origins of microgrewiapine C and congeners suggests that further phytochemical investigations are warranted.

Polarization in social media assists influencers to become more influential: analysis and two inoculation strategies.

This work explores simulations of polarized discussions from a general and theoretical premise. Specifically the question of whether a plausible avenue exists for a subgroup in an online social network to find a disagreement beneficial and what that benefit could be. A methodological framework is proposed which represents key factors that drives social media engagement including the iterative accumulation of influence and the dynamics for the asymmetric treatment of messages during a disagreement. It is shown that prior to a polarization event a trend towards a more uniform distribution of relative influence is achieved which is then reversed by the polarization event. The reasons for this reversal are discussed and how it has a plausible analogue in real world systems. A pair of inoculation strategies are proposed which aim at returning the trend towards uniform influence across users while refraining from violating user privacy (by remaining topic agnostic) and from user removal operations.

Well-defined Ti4 pre-catalysts for the ring-opening polymerisation of lactide.

The synthesis and full characterisation of four discrete tetrametallic titanium complexes is reported. These well-defined compounds are isostructural in the solid state and share the same general formula: Ti4(µ-O)2L4 (L = 1, 2, 3 or 4). Using a combination of NMR techniques the complexes are found to be stable in solution, even at elevated temperatures. Further studies show that the carboxylate moieties of the supporting amine bis(phenolate) ligands can be displaced by a more strongly coordinating solvent. This reversible process causes the coordinatively saturated Ti4(µ-O)2L4 complexes to separate into two Ti2(µ-O)L2 subunits which we envisaged would be catalytically active. Proof-of-concept experiments establish that all four of these complexes display catalytic activity in the ring-opening polymerisation of rac-lactide. These aggregates can therefore be viewed as air and moisture stable pre-catalysts for a range of reactions.