In our newest pre-print posted online today, we continue our explorations of reactions enabled by the W⁰/W^II redox manifold and report the discovery of a mild method for selectively isomerizing γ,δ-unsaturated amides into their β,γ-unsaturated counterparts without “over-isomerization” into conjugation. By controlling the ligand environment around the metal center, stereoselectivity can be controlled to favor either the (Z)- or the (E)-isomer. Though organometallic synthesis, we were able to shed light on some details of the reaction mechanism, highlighted by synthesis of a stable W^II(π-Allyl)(OAc) complex that can converted in situ to a W^II(π-allyl)(H) species, thereby intercepting a proposed intermediate in the catalytic cycle. Congrats to Tanner, Camile, and Raul!

For a link to the pre-print in ChemRxiv, click here: https://chemrxiv.org/engage/chemrxiv/article-details/63bfba1c741025af42ec927c