Dasgupta, AyanStefkova, KatarínaBabaahmadi, RasoolGierlichs, LukasAriafard, AlirezaMelen, Rebecca L.2025-12-162025-12-161433-7851PubMed:32485034ORCID:/0000-0003-2383-6380/work/197987403https://hdl.handle.net/1885/733795591Herein we report a facile, mild reaction protocol to form carbon–carbon bonds in the absence of transition metal catalysts. We demonstrate the metal-free alkenylation reactions of aryl esters with α-diazoesters to give highly functionalized enyne products. Catalytic amounts of tris(pentafluorophenyl)borane (10–20 mol %) are employed to afford the C=C coupled products (31 examples) in good to excellent yields (36–87 %). DFT studies were used to elucidate the mechanism for this alkenylation reaction.A.D., K.S., and R.L.M. acknowledge the EPSRC for an Early Career Fellowship for funding (EP/R026912/1). A.A. and R.B. thank the Australian Research Council (ARC) for project funding (DP180100904), and the Australian National Computational Infrastructure and the University of Tasmania for the generous allocation of computing time.5en© 2020 The Authors.alkenylationdiazoestersmetal-free catalysistris(pentafluorophenyl)borane202010.1002/anie.20200717685087964235