Exploiting Visible Light Triggered Formation of trans-Cyclohexene for the Contra-thermodynamic Protection of Alcohols

Article Chemistry, Multidisciplinary

Efforts toward Synthetic Photosynthesis: Visible Light-Driven CO2 Valorization

Timothy D. Schoch et al.

Summary: Current methods of urethane preparation require high-energy and often toxic or cumbersome molecules, making the process exergonic. CO2 aminoalkylation using olefins and amines provides an endergonic alternative. We developed a moisture-tolerant method that utilizes visible light energy to drive this endergonic process, using sensitized arylcyclohexenes. These molecules convert photon's energy into strain energy upon olefin isomerization, significantly enhancing alkene basicity and allowing for sequential protonation and interception of ammonium carbamates. Through optimization and amine scope evaluation, we successfully demonstrated the transcarbamoylation of an arylcyclohexyl urethane with various alcohols, forming more general urethanes and regenerating the arylcyclohexene. This closure of the energetic cycle results in water as the stoichiometric byproduct.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2023)

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Review Chemistry, Multidisciplinary

Advances in the E → Z Isomerization of Alkenes Using Small Molecule Photocatalysts

Tomas Nevesely et al.

Summary: Geometrical E → Z alkene isomerization, a critical topic in organic photochemistry, has seen significant advancements in recent years. By utilizing energy transfer catalysis, directed isomerization of alkenes can be achieved. This review summarizes the progress in the field of geometric alkene isomerization enabled by energy transfer catalysis from 2000 to 2020, and discusses the reaction mechanisms, induction models, and applications in total synthesis and regioselective reactions.

CHEMICAL REVIEWS (2022)

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Article Chemistry, Multidisciplinary

Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers

Jong-Hwa Shon et al.

Summary: This study demonstrates that strong bis-cyclometalated iridium photoreductants with specific ligands can achieve high-yielding photoredox transformations of challenging substrates with very simple reaction conditions requiring only a single sacrificial reagent.

CHEMICAL SCIENCE (2021)

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Article Chemistry, Organic