The synthesis of tertiarya lkyl fluorides through af ormal radical deoxyfluorination process is described herein. This light-mediated, catalyst-free methodology is fast and broadly applicable allowing for the preparation of CÀFb onds from (hetero)benzylic, propargylic,a nd non-activated tertiarya lcohold erivatives. Preliminary mechanistic studies support that the key step of the reactioni st he single-electron oxidation of cesium oxalates-which are readily available from the corresponding tertiary alcohols-with in situ generated TEDA 2+ + C (TEDA: N-(chloromethyl)triethylenediamine), ar adical cation derived from Selectfluor.

In this paper, we present a short and convenient synthesis of the natural product Harzialactone A and its three stereoisomers. In a three‐step synthesis starting from cheap and commercially available benzaldehyde, we created the small polyketidic compound with full control over its two stereogenic centers. To this end, we employed a chiral building block previously described by us, introducing the first stereogenic center through a Horner–Wittig reaction. The second stereogenic center was installed via stereocontrolled syn‐ or anti‐reduction with the corresponding β‐hydroxy ketone intermediates. Upon ozonolysis followed by oxidation the natural product and its stereovariants were produced with excellent enantio‐ and diastereopurities.