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Boron-Enabled Geometric Isomerization of Small Alkene Fragments via Selective Energy Transfer Catalysis
preprintsubmitted on 13.03.2020, 17:28 and posted on 16.03.2020, 11:24 by John James Molloy, Michael Schäfers, Max Wienhold, Tobias Morack, Constantin G. Daniliuc, Ryan Gilmour
The mammalian visual cycle epitomizes the importance of complex polyenes in biology. However, isomerization-based strategies to enable the sterodivergent construction of these important biomolecules from geometrically defined alkene linchpins remain conspicuously underdeveloped. Mitigating the thermodynamic constraints inherent to isomerization is further frustrated by the considerations of atom efficiency in idealized low molecular precursors. Herein, we report a general ambiphilic C3 scaffold that can be isomerized and bi-directionally extended. Predicated on highly efficient triplet energy transfer, the selective isomerization of β-15 borylacrylates is contingent on the participation of the boron p-orbital in the substrate chromophore. Rotation of the C(sp2)-B bond by 90° in the product renders re-excitation inefficient and endows directionality. This subtle stereoelectronic gating mechanism enables the stereocontrolled syntheses of well-defined retinoic acid derivatives.