Recent Advances in Carbonyl‐Photoredox/Transition Metal Dual Catalysis

Abstract

Organic transformations using carbonyl‐photoredox/metal dual catalysis have attracted much attention in recent years. Abundant and inexpensive carbonyl photosensitizers effectively serve as single electron, energy or hydrogen atom transfer agents to induce metal‐catalyzed cross‐coupling and dicarbofunctionalization of olefins. This review covers literature reports of metal‐catalyzed photocatalytic coupling reactions from 2020 to mid‐2023, with a focus on C−C (C(sp3)−C(sp3), C(sp3)−C(sp2), C(sp2)−C(sp2), C(sp2)−C(sp)) and C‐heteroatom (C(sp3)−S, C(sp3)−N, C(sp2)−O, C(sp2)−S, C(sp2)−P, C(sp2)−B) bond forming reactions.

Quinone-Initiated Photocatalytic Enantioselective Giese Radical Addition with Ethers, Thioethers, Amines, and Alkanes

“…This enables the facile generation of active radical species, avoiding the requirement of prefunctionalization and harsh reaction conditions. To date, a few classes of HAT photocatalysts have been successfully developed, including neutral eosin Y (EY), , decatungstate (TBADT), − aromatic ketones and quinones, − uranyl cation, , and antimony-oxo porphyrin . The synergistic catalysis of HAT photocatalysts and chiral catalysts (Scheme a, right) provides an elegant route for asymmetric Giese reactions with various inert C(sp 3 )–H bonds.…”

“…Quinones are potential alternatives as HAT photocatalysts to activate inert C(sp 3 )–H bonds, − and may also interact with chiral Lewis acid catalysts, thereby aiding in enantiocontrol. Chiral N , N ′-dioxide/metal complex catalysts − developed by our group have shown effective ability in several asymmetric radical reactions. − We envisioned that the quinone and chiral N , N ′-dioxide/metal Lewis acid cooperative catalysis, which is underdeveloped in asymmetric Giese reactions with inert C(sp 3 )–H donors, might present unique opportunities to mediate enantio-induction.…”