Catalytic asymmetric C–C cross-couplings enabled by photoexcitation

Photocatalytic C(sp3) radical generationviaC–H, C–C, and C–X bond cleavage

“…It is notable that recently, the same group reported an asymmetric C-C cross-coupling between aliphatic silanes and allylic alcohols, in which the photoexcitable allylic Ir(III) complex mediated the Rc formation and the chiral induction for the C-C bond-forming step. 216 As explored in Fensterbank's and Kano's studies and others, anionic hypervalent silicate could generate the Rc under comparably milder conditions due to its anionic character. On this basis, two different types of silicates were applied in photoredox chemistry.…”

Boron, silicon, nitrogen and sulfur-based contemporary precursors for the generation of alkyl radicals by single electron transfer and their synthetic utilization

“…Very recently, Melchiorre and co-workers disclosed an elegant approach for the asymmetric photochemical allylation from allylic alcohol derivatives 160 and alkyl–DHPs 161 in the presence of [Ir(cod)Cl] 2 and a ( S )-phosphoramidite-olefin ligand. 113 The allylated products 162 were obtained in good yields with good selectivities (Scheme 57).…”

Recent advances in iridium-catalyzed enantioselective allylic substitution using phosphoramidite-alkene ligands

“…Mazzarella and Melchiorre reported Ir-catalyzed enantioselective allylic alkylation by photoexcitation (Scheme 27). 73…”