The first visible-light driven aerobic oxidation for the direct selenation of (hetero)arenes has been developed at room temperature, providing an eco-friendly, atom-economical protocol to prepare unsymmetrical selenides from easily accessible diselenides.
Substrates
in excited state differ significantly from the corresponding
ground state so that they are treated as different chemical species
with diverse physical properties and chemical reactivity. Therefore,
applying photocatalytic systems to activate substrates becomes increasingly
popular. Although photosensitizers serve as the core of the photocatalytic
reaction, the design of a photosensitizer has not been taken for granted.
By modifying ligands of organometallic complexes to optimize properties
of photosensitizers, we successfully achieved a series of iridium
complexes with long excited triplet-state lifetime, high triplet excited-state
energy, strong absorption, and robust stability. The efficacies of
the prepared iridium complexes as photosensitizers were evaluated
toward various challenging photocycloaddition reactions (e.g., thia-Paternò–Büchi
reaction and multicomponent one-pot aza-photocyclization) between
heterocyclic compound maleimides and unsaturated moieties that are
not efficient to complete with well-established photosensitizers.
A direct, redox-neutral, highly atom-economical and metal-free aerobic method for the synthesis of multi-substituted olefins via simply coupling ammonium thiocyanate with activated ketones is described.
The aerobic dehydrogenative
cyclization of alkenes with easily
accessible diselenides facilitated by visible light is reported. Notably,
the features of this transition-metal-free protocol are pronounced
efficiency and practicality, good functional group tolerance, atom
economy, and high sustainability, since ambient air and visible light
are adequate for the clean construction of five- and six membered
heterocycles in yields of up to 98%.
The first visible-light enabled metal-free aerobic protocol for one-pot synthesis of benzoin bis-ethers from alkenes and alcohols has been developed at room temperature.
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