The hydrofluorination of enolizable ynones with AgF in t-BuOH/DMF is reported. The formation of furans as side products can be suppressed using 2,2'-biphenol. The corresponding β-fluoroenones were obtained with good Z-selectivity. A variety of functional groups are tolerated. β-Fluoroenones are vinylogous acid fluorides whose hydrolysis to vinylogous acids can be avoided under the reported reaction conditions. The asymmetric 1,2-reduction of β-fluoroenones to 3-fluoroallylic alcohols is possible with pinacolborane and a Ni(0) catalyst prepared from a pyrimidyloxazoline ligand.

Due to their high density of functional groups, vicinal tricarbonyl compounds are versatile building blocks for the synthesis of complex target molecules. Methods for their preparation and their use in stereoselective CC bond formations, as well as for the synthesis of heteroaromatics, are summarised for the period 2006-2016. Several examples for their applications in natural product synthesis (awajanomycin, cladoniamide, wailupemycin) are presented. 1 Introduction 2 Preparation of Vicinal Tricarbonyl Compounds 3 Use in Stereoselective CC Bond Formations 4 Use for the Synthesis of Heteroaromatics 5 Examples from Natural Product Synthesis 6 Conclusion Key words vicinal tricarbonyl compounds, stereoselective synthesis, natural products, total synthesis, regioselectivity Lars Selter (from left to right) was born in Berlin, Germany in 1989. He studied chemistry at the Freie Universität Berlin and received his B.Sc. degree in 2011 and his M.Sc. degree in 2013 under the supervision of Prof. H.-U. Reißig. Currently, he is working as a Ph.D. student at the Philipps-Universität Marburg under the guidance of Prof. U. Koert focusing on regioselective CC bond formation on vicinal tricarbonyl compounds. Lukas Zygalski was born in Rotenburg/Fulda, Germany in 1990. He completed his B.Sc. degree in 2013 and his M.Sc. degree (specialisation in organic chemistry) in 2016 under the supervision of Prof. U. Koert at the Philipps-Universität Marburg. Currently, he is working there as a Ph.D. student focusing on natural product synthesis. Eric Kerste was born in Rotenburg/Fulda, Germany in 1990. He completed his B.Sc. degree in 2013 and his M.Sc. degree (specialisation in organic chemistry) in 2016, both under the supervision of Prof. U. Koert at the Philipps-Universität Marburg. Currently, he is working there as a Ph.D. student focusing on natural product synthesis based on vicinal diketo esters. Ulrich Koert was born in Hanau, Germany in 1961. He studied chemistry at the Goethe Universität in Frankfurt where he obtained his Ph.D. in

A rhodium catalyzed allylic cyanation of 3‐fluoroallylic trifluoroacetates with TMSCN and a bulky phosphite ligand gives 3‐fluoroallylic nitriles with a good substrate scope and high Z/E‐selectivity. For dialkylated substrates the fluorine substituent controls the regioselectivity in favor of the distal product. For the stereoselectivity of the allylic cyanation selected scalemic substrates showed inversion of the stereocenter and some or no stereoerosion.