Executive Summary : | The proposal focuses on photocatalytic redox-neutral syntheses of functionalized organic molecules using unactivated alkenes and other molecules. It aims to create α-amino acids, which are valuable synthetic building blocks for peptides and active drug molecules. The blue LED-irradiated excited Ir(III)* undergoes a SET event with α-amino acids, forming an alkyl radical and removing hydrogen and carbon dioxide. This radical then attacks the alkene, forming an α-amine radical that reacts with in situ generated CO₂ and H radicals to produce the desired product. The metallaphotoredox mediated carboamination of unactivated alkene is exciting, as it allows for difunctionalization across a double bond and formation of both C–C and C–N bonds in a redox-neutral manner. A standard substrate is N-tethered alkene benzenesulfonamide, with a base added for proton abstraction. The Ir(III) metallaphotoredox catalyst generates a nitrogen-bearing radical, which is then converted into a five-membered N-heterocycle and tertiary carbon radical. The proposal also proposes a 1,6 carbotrifluoromethylation of alkenes with trifluoromethylsulfonyl chloride as a CF₃ surrogate and imidazo heterocycle for another coupling partner under visible light-induced photoredox catalysis. The photo-excited Ru(II) photocatalyst undergoes single-electron reduction of CF₃SO₂Cl to give trifluoromethyl radical, which can attack the alkene and form a secondary benzylic radical. Lastly, the proposal proposes a photocatalytic redox neutral hydrofunctionalization reaction of unsaturated amides to construct an oxazoline-containing ring. The excited photocatalyst participates in SET with allylic amide, generating cation radical and alkyl radical. |