SmI-Catalyzed Intermolecular Coupling of Cyclopropyl Ketones and Alkynes: A Link between Ketone Conformation and Reactivity.

The archetypal single electron transfer reductant, samarium(II) diiodide (SmI, Kagan's reagent), remains one of the most important reducing agents and mediators of radical chemistry after four decades of widespread use in synthesis. While the chemistry of SmI is very often unique, and thus the reagent is indispensable, it is almost invariably used in superstoichiometric amounts, thus raising issues of cost and waste. Of the few reports of the use of catalytic SmI, all require the use of superstoichiometric amounts of a metal coreductant to regenerate Sm(II). Here, we describe a SmI-catalyzed intermolecular radical coupling of aryl cyclopropyl ketones and alkynes. The process shows broad substrate scope and delivers a library of decorated cyclopentenes with loadings of SmI as low as 15 mol %. The radical relay strategy negates the need for a superstoichiometric coreductant and additives to regenerate SmI. Crucially, our study uncovers an intriguing link between ketone conformation and efficient cross-coupling and thus provides an insight into the mechanism of radical relays involving SmI. The study lays further groundwork for the future use of the classical reagent SmI in contemporary radical catalysis.