Turning to a new part of the periodic table this week, we describe our first foray into the use of W(0)/W(II) catalysis for migratory alkene functionalization. By taking advantage of the ability of tungsten to toggle between six- and seven-coordinate geometries upon oxidative addition, we are able to isomerize an alkene to a classically disfavored position through a metallacycle contraction process, where it is primed for carbonylative functionalization. Bravo to Tanner and Zi-Yang (Nick) from our group; our computational collaborators Will and Yu from the Liu group at the University of Pittsburgh; and X-ray crystallographer extraordinaire Milan from UCSD.

For a link to the ChemRxiv pre-print, click here: https://chemrxiv.org/articles/preprint/Low-Valent_Tungsten_Redox_Catalysis_Enables_Controlled_Isomerization_and_Carbonylative_Functionalization_of_Alkenes/14362238