A chiral, ammonium ylide based access to tetrasubstituted 2,3‐dihydrofurans starting from readily available benzylidene dicarbonyls and bromo acetophenones has been developed. The products are obtained in moderate to good yields with excellent diasteroselectivity and good to excellent enantioselectivity (up to 99:1 e.r.). The employed chiral amine can be recovered in near quantitative yield. The transformation can be run as a three‐component one‐pot reaction, generating the ammonium salt and ylide in situ. The scope of this reaction includes 17 new dihydrofurans with aromatic or heteroaromatic substituents.

An ammonium ylide mediated access towards trans‐β,γ‐disubstituted, all‐trans‐α,β,γ‐trisubstituted, and α,α,β,γ‐tetrasubstituted γ‐butyrolactones bearing a broad variety of functionalities was developed. Starting from widely accessible benzylidene Meldrum's acid derivatives and α‐bromo carbonyl compounds, γ‐butyrolactones were obtained in yields between 32–99% with up to excellent diastereoselectivities (>95:5) via a DABCO‐mediated [2+1] annulation. Utilization of enantiomerically pure cinchona alkaloid derivatives enables the first asymmetric ammonium ylide mediated method to provide (3R, 4R)‐β,γ‐disubstituted and (2R, 3R, 4R)‐α,β,γ‐trisubstituted γ‐butyrolactones in moderate to good yields with up to very good enantiomeric ratios (97:3). The scalability of the transformation was proven while determining the absolute configuration.

The inside cover picture, designed by Irene Küberl from the Institute of Bioorganic Chemistry in Düsseldorf/Jülich, illustrates the utilization of Cinchona alkaloid derivatives in the first asymmetric ammonium ylide mediated transformation towards highly enantiomerically enriched di‐, tri‐, and even tetrasubstituted γ‐butyrolactones. Details of this work can be found in the full paper on pages 2385–2396 (T. Drennhaus, L. Öhler, S. Djalali, S. Höfmann, C. Müller, J. Pietruszka, D. Worgull, Adv. Synth. Catal. 2020, 362, 2385–2396; DOI: 10.1002/adsc.202000039).