Ketones from Nickel-Catalyzed Decarboxylative, Non-Symmetric Cross-Electrophile Coupling of Carboxylic Acid Esters

A new strategy for the synthesis of ketones is presented based upon the decarboxylative coupling of N-hydroxyphthalimide (NHP) esters with S-2-pyridyl thioesters. The reactions are selective for the cross-coupled product because NHP esters act as radical donors and the thioesters act as acyl donors. The reaction conditions are general and mild, with over 40 examples presented, including larger fragments and the 20-mer peptide Exendin(9-39) on solid support.