The broad synthetic utility of organoboron compounds stems from their ready ability to undergo 1,2-migrations. Normally, such shifts are induced by α-leaving groups or by reactions of alkenyl boronates with electrophiles. Herein, we present a new strategy to induce 1,2-metalate rearrangements, via ring expansion of vinylcyclopropyl boronate complexes activated by electrophiles. This leads to a cyclopropane-stabilized carbocation, which triggers ring expansion and concomitant 1,2-metalate rearrangement. This novel process delivers medicinally relevant 1,2-substituted cyclobutyl boronic esters with high levels of diastereoselectivity. A wide range of organolithiums and Grignard reagents, electrophiles, and vinylcyclopropyl boronic esters can be used. The methodology was applied to a short, stereoselective synthesis of (±)-grandisol. Computational studies indicate that the reaction proceeds via a nonclassical carbocation followed by anti-1,2-migration.

Five new group 4 ansa-bridged permethylindenyl complexes with either a dimethylsilane bridge or a tetramethyldisilane bridge have been synthesised and fully characterised. These complexes were supported on a hydrocarbon insoluble polymethylaluminoxane (sMAO) and the slurry-phase ethylene polymerisation performance was investigated. The highest activity was achieved using Me 2 SB(Cp Me ,I*)Zr( CH2SiMe3)2 (8042 kgPE molZr -1 h -1 bar -1 at 60 °C) but a decrease in activity was observed with an increase in the length of the bridge. DSC analysis of the polymers revealed the production of HDPE with minimal branching and defects, while SEM showed the production of polymer particles with commercially desirable uniform, 'popcorn', morphology. GPC analysis showed the production of polyethylenes with Mw < 570 kg mol -1 at 80 °C. In addition, Me 2 SB(Cp,I*)Zr(CH2SiMe3)2 was immobilised on MAO modified layered double hydroxide (LDHMAO). The slurry-phase polymerisation activity of Me 2 SB(Cp,I*)Zr(CH2SiMe3)2 on this support system was similar to the sMAO support, however the polymer morphology was much less uniform.

The identification of the beneficial pharmacokinetic properties of aza-spirocycles has led to the routine incorporation of these highly rigid and three-dimensional structures in pharmaceuticals. Herein, we report an operationally simple synthesis of spirocyclic dihydropyridines via an electrophile-induced dearomative semi-pinacol rearrangement of 4-(1′-hydroxycyclobutyl)pyridines. The various points for diversification of the spirocyclization precursors, as well as the synthetic utility of the amine and ketone functionalities in the products, provide the potential to rapidly assemble medicinally relevant spirocycles.