Pd/BIPHEPHOS is an Efficient Catalyst for the Pd‐Catalyzed <i>S</i>‐Allylation of Thiols with High <i>n</i>‐Selectivity

Abstract

The Pd-catalyzed <i>S</i>-allylation of thiols with stable allylcarbonate and allylacetate reagents offers several advantages over established reactions for the formation of thioethers. We could demonstrate that Pd/BIPHEPHOS is a catalyst system which allows the transition metal-catalyzed <i>S</i>-allylation of thiols with excellent <i>n</i>-regioselectivity. Mechanistic studies showed that this reaction is reversible under the applied reaction conditions. The excellent functional group tolerance of this transformation was demonstrated with a broad variety of thiol nucleophiles (18 examples) and allyl substrates (9 examples), and could even be applied for the late-stage diversification of cephalosporins, which might find application in the synthesis of new antibiotics.