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Authors: Zähringer, Till J. B.
Wienhold, Max
Gilmour, Ryan
Kerzig, Christoph
Title: Raw data for "Direct observation of triplet states in the isomerization of alkenylboronates by energy transfer catalysis"
Online publication date: 19-Sep-2023
Year of first publication: 2023
Language: english
Abstract: Alkenylboronates are versatile building blocks for stereocontrolled synthesis owing to the traceless nature of the boron group that can be leveraged to achieve highly selective geometric isomerization. Using thioxanthone as an inexpensive photocatalyst, their photoisomerization continues to provide an expansive platform for stereodivergent synthesis, particularly in the construction of bioactive polyenes. Although mechanistic investigations are consistent with light−driven energy transfer, direct experimental evidence remains conspicuously absent. Herein, we report a rigorous mechanistic investigation using two widely used alkenylboronates alongside relevant reference compounds. Through the combination of irradiation experiments, transient absorption spectroscopic studies, kinetic modeling, and DFT calculations with all isomers of the model compounds, it has been possible to unequivocally detect and characterize the perpendicular triplet generated by energy transfer. Our results serve not only as a blueprint for mechanistic studies that are challenging with organic sensitizers, but these guidelines delineated have also enabled the development of more sustainable reaction conditions: for the first time, efficient organocatalytic isomerization under sunlight irradiation has become feasible.
DDC: 540 Chemie
540 Chemistry and allied sciences
Institution: Johannes Gutenberg-Universität Mainz
Department: FB 09 Chemie, Pharmazie u. Geowissensch.
Place: Mainz
Version: Original work
Publication type: Datensammlung
License: CC BY
Information on rights of use:
Relations: is source of 10.1021/jacs.3c07678
Appears in collections:JGU-Forschungsdaten

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raw_data_for_direct_observati-20230915085237535.zipDFT output for optimized structures27.36 MBZIPView/Open
raw_data_for_direct_observati-20230915085320148.zipRaw data for figures in the main manuscript546.6 kBZIPView/Open