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Deconstructing the Catalytic, Vicinal Difluorination of Alkenes: HF-Free Synthesis and Structural Study of p‑TolIF2

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journal contribution
posted on 28.07.2017 by Jérôme C. Sarie, Christian Thiehoff, Richard J. Mudd, Constantin G. Daniliuc, Gerald Kehr, Ryan Gilmour
Recently, contemporaneous strategies to achieve the vicinal difluorination of alkenes via an I­(I)/I­(III) catalysis manifold were independently reported by this laboratory and by Jacobsen and co-workers. Both strategies proceed through a transient ArI­(III)­F2 species generated by oxidation of the ArI catalyst. Herein, an efficient synthesis of p-TolIF2 from p-TolI and Selectfluor is presented, together with a crystallographic and spectroscopic study. To mitigate safety concerns and simplify reaction execution, an HF-free protocol was devised employing CsF as a substitute fluoride source. The study provides insight into the initial I­(I)→I­(III) oxidation stage of the catalytic protocol using Selectfluor.