Photochemical Synthesis of Acyl Fluorides Using Copper-Catalyzed Fluorocarbonylation of Alkyl Iodides.

Acyl fluorides are important reagents due to their unique balance between reactivity and stability. Here, we report a copper-catalyzed carbonylative coupling strategy for synthesizing acyl fluorides under photoirradiation. Alkyl iodides were transformed in high yields into acyl fluorides by using a commercially available copper precatalyst (CuBr·SMe) and a readily available fluoride salt (KF) at ambient temperature and mild CO pressure (6 atm) under blue light irradiation.

Light-Mediated Synthesis of Aliphatic Anhydrides by Cu-Catalyzed Carbonylation of Alkyl Halides.

Acid anhydrides are valuable in the chemical industry for their role in synthesizing polymers, pharmaceuticals, and other commodities, but their syntheses often involve multiple steps with precious metal catalysts. The simplest anhydride, acetic anhydride, is currently produced by two Rh-catalyzed carbonylation reactions on a bulk scale for its use in synthesizing products ranging from aspirin to cellulose acetate. Here, we report a light-mediated, Cu-catalyzed process for producing aliphatic, symmetric acid anhydrides directly by carbonylation of alkyl (pseudo)halides in a single step without any precious metal additives.

Preparation of Potassium Acyltrifluoroborates (KATs) from Carboxylic Acids by Copper-Catalyzed Borylation of Mixed Anhydrides.

We report the preparation of potassium acyltrifluoroborates (KATs) from widely available carboxylic acids. Mixed anhydrides of carboxylic acids were prepared using isobutyl chloroformate and transformed to the corresponding KATs using a commercial copper catalyst, B (pin) , and aqueous KHF . This method allows for the facile preparation of aliphatic, aromatic, and amino acid-derived KATs and is compatible with a variety of functional groups including alkenes, esters, halides, nitriles, and protected amines.

Annulative Morita-Baylis-Hillman reaction to synthesise chiral dibenzocycloheptanes.

We describe the first metal-free and organocatalytic strategy to access highly functionalised dibenzocycloheptanes a phosphine-promoted annulative Morita-Baylis-Hillman (MBH) reaction. The method is manipulated to access to chiral dibenzocycloheptanes as well. This work represents a rare entry for the construction of seven-membered carbocycles the MBH route.

Palladium-Catalyzed Intramolecular Trost-Oppolzer-Type Alder-Ene Reaction of Dienyl Acetates to Cyclopentadienes.

A new approach to the synthesis of highly substituted cyclopentadienes, indenes, and cyclopentene-fused heteroarenes by means of the Pd-catalyzed Trost-Oppolzer-type intramolecular Alder-ene reaction of 2,4-pentadienyl acetates is described. This unprecedented transformation combines the electrophilic features of the Tsuji-Trost reaction with the nucleophilic features of the Alder-ene reaction. The overall outcome can be perceived as a hitherto unknown "acid-free" iso-Nazarov-type cyclization.