Decarboxylative Alkylation of Carboxylic Acids with Easily Oxidizable Functional Groups Catalyzed by an Imidazole-Coordinated Fe Cluster under Visible Light Irradiation.

Decarboxylative alkylation of carboxylic acids with easily oxidizable functional groups such as phenol and indole functionalities was achieved using a catalytic amount of basic iron(III) acetate, Fe(OAc)(OH), in the presence of benzimidazole under 427 nm LED irradiation. Kinetic analyses of this catalytic reaction revealed that the reaction rate is first-order in alkenes and is linearly correlated with the light intensity; the faster reaction rate for the benzimidazole-ligated species was consistent with the increased absorbance in the visible light region. Wide functional group tolerance for the easily oxidizable groups is ascribed to the weak oxidation ability of the in situ-generated oxo-bridged iron clusters compared with other iron(III) species.

Studies towards the Enantioselective Synthesis of Cryptowolinol via Pd-Catalyzed C(sp)-H Arylation/Parallel Kinetic Resolution.

We report a model study towards the enantioselective synthesis of the dibenzopyrrocoline alkaloid (-)-cryptowolinol. The key step involves a challenging enantioselective Pd-catalyzed C(sp)-H arylation performed with a chiral NHC ligand, which proceeds via parallel kinetic resolution (PKR). A very efficient PKR process was achieved on a deoxygenated model substrate and was successfully transposed to a potential intermediate en route to (-)-cryptowolinol.

Cerium(IV) Carboxylate Photocatalyst for Catalytic Radical Formation from Carboxylic Acids: Decarboxylative Oxygenation of Aliphatic Carboxylic Acids and Lactonization of Aromatic Carboxylic Acids.

We found that generated cerium(IV) carboxylate generated by mixing the precursor Ce(OBu) with the corresponding carboxylic acids served as efficient photocatalysts for the direct formation of carboxyl radicals from carboxylic acids under blue light-emitting diodes (blue LEDs) irradiation and air, resulting in catalytic decarboxylative oxygenation of aliphatic carboxylic acids to give C-O bond-forming products such as aldehydes and ketones. Control experiments revealed that hexanuclear Ce(IV) carboxylate clusters initially formed in the reaction mixture and the ligand-to-metal charge transfer nature of the Ce(IV) carboxylate clusters was responsible for the high catalytic performance to transform the carboxylate ligands to the carboxyl radical. In addition, the Ce(IV) carboxylate cluster catalyzed direct lactonization of 2-isopropylbenzoic acid to produce the corresponding peroxy lactone and γ-lactone via intramolecular 1,5-hydrogen atom transfer (1,5-HAT).