CC BY-NC 4.0 UnportedGe, YaoYe, FeiLiu, JiawangYang, JiSpannenberg, AnkeJiao, HaijunJackstell, RalfBeller, Matthias2021-09-022021-09-022020https://oa.tib.eu/renate/handle/123456789/6666https://doi.org/10.34657/5713The first general and regioselective Pd-catalyzed cyclocarbonylation to give α-methylene-β-lactones is reported. Key to the success for this process is the use of a specific sterically demanding phosphine ligand based on N-arylated imidazole (L11) in the presence of Pd(MeCN)2Cl2 as pre-catalyst. A variety of easily available alkynols provide under additive-free conditions the corresponding α-methylene-β-lactones in moderate to good yields with excellent regio- and diastereoselectivity. The applicability of this novel methodology is showcased by the direct carbonylation of biologically active molecules including natural products. © 2020 The Authors. Published by Wiley-VCH GmbHenghttps://creativecommons.org/licenses/by-nc/4.0/540alkynolcarbonylationcatalysispalladiumphosphineα-methylene-β-lactoneArticle