CATALYTIC CARBONYLATIONS OF ARYL ELECTROPHILES AND ALKENES VIA THERMAL AND PHOTOCHEMICAL ACTIVATION

I. Metal-Catalyzed Carbonylations of Aryl Electrophiles and AlkenesAn overview of challenges related to general methods of aminocarbonylation of aryl electrophiles and hydrocarbonylation of unactivated olefins is presented. Current methodology utilizing visible light irradiation and first-row transition metals are discussed for the aminocarbonylation of aryl halides. Cobalt-catalyzed hydrocarbonylation of alkenes is also described.II. Cobalt-Catalyzed Aminocarbonylation of Aryl HalidesThe catalytic aminocarbonylation of (hetero)aryl bromides and chlorides with a simple cobalt catalyst under visible light irradiation is presented. A broad scope of aryl substitution and functionality is successful with a wide range of amine nucleophiles. III. Deaminative Aminocarbonylation Aryl Trialkylammonium SaltsCobalt-catalyzed aminocarbonylation of aryl trialkylammonium salts is demonstrated. Selective cleavage of the C(sp2)–N bond delivers diverse benzamides suitable to late-stage functionalization of drug compounds and telescoped reactivity from primary and tertiary anilines. Mechanistic experiments and DFT calculations detail a carbonyl ligand photodissociation and SNAr-type oxidative addition.IV. Cobalt-Catalyzed Hydroaminocarbonylation of Unactivated OlefinsHydroaminocarbonylation of various substituted alkenes with a simple cobalt catalyst is described. High chemo- and regioselectivity deliver aliphatic amides in high yields from a broad scope of 1° and 2° alkyl amine nucleophiles or ammonia. A formal hydroaminomethylation via addition of silane reagents can deliver aliphatic amines via reduction of the amides generated in situ. A commentary on mechanistic experiments, DFT calculations, and a mechanistic comparison to hydroformylation with this classic cobalt catalyst is also provided.V. Palladium-Catalyzed Synthesis of Anhydrides via Hydrocarbonylation of OlefinsAn atom-economical carbonylative synthesis of symmetric aliphatic anhydrides catalyzed by low loading of palladium is explained. Carboxylic acids perform as an acid equivalent to generate palladium hydride intermediates, as well as the nucleophilic coupling partner. Catalytic additives are studied and the relation to regioselectivity is investigated.