Development of a Phototriggered Diradical Phosphoamination Strategy of Alkenes.

Aminophosphonates serve as extremely important moieties with respect to their activities in biological systems. However, incorporating a Nitrogen and Phosphorus moiety by conventional techniques in ionic mode is usually associated with extensive prefunctionalization of the substrates, employing harsh conditions and reagents that limit the viability of these methods. Introducing both of these components as radicals may be a viable option.

Photocascade chemoselective controlling of ambident thio(seleno)cyanates with alkenes via catalyst modulation.

Controlling the ambident reactivity of thiocyanates in reaction manifolds has been a long-standing and formidable challenge. We report herein a photoredox strategy for installing thiocyanates and isothiocyanates in a controlled chemoselective fashion by manipulating the ambident-SCN through catalyst modulation. The methodology allows redox-, and pot-economical 'on-demand' direct access to both hydrothiophene and pyrrolidine heterocycles from the same feedstock alkenes and bifunctional thiocyanomalonates in a photocascade sequence.

A two carbon homologation of Friedel-Crafts alkylation enabled by photochemical alkene stitching: modular assembly of cyclolignans.

Herein we report an efficient two-carbon homologated variant of Friedel-Crafts alkylation photochemical radical alkene stitching. Readily available feedstock alkenes are used as bridges between photogenerated alkyl radicals and arenes, opening a route to γ-aryl-carbonyls for chemo-divergent access to aryltetralone and γ-lactones, a gateway to 2,7'-cyclolignans.

Zinc acetate-promoted blocking of the ATRA process with alkyl halides enabling photochemical alkylamination of olefins.

Organic photoredox-catalyzed alkylamination of olefins is performed with alkyl halides and nitrile solvent by blocking the traditional photoredox-ATRA process with Zn(OAc). A range of carbon-centered radicals (α-alkylcarbonyl, benzyl, cyanomethyl) are effectively participating in this strategy giving rise to versatile carboamination products with high synthetic value.