A chemoselective rhodium(III)-catalyzed cascade annulation for the construction of the indolizinone and quinolizinone scaffolds is developed. Diversification of peptidomimetics and oligopeptides is achieved in a rapid and step-economical manner through the combination of Ugi reaction and microwave-assisted rhodium(III)-catalyzed intramolecular annulation via C(sp 2 )-H activation without installing a directing group.

Figure 1. Structures of furan derivatives 1-5 and anhydrides 6-7.Scheme1.Prior work on ROMP of fully bio-based monomers prepared from itaconic anhydride.Scheme2.Synthesis of monomers 13 a-c.Scheme3.ROMP of monomers 13 a-c with Grubbs catalysts 9 and 14.

The inside cover picture, designed by Liangliang Song from the group of Erik V. Van der Eycken, illustrates a chemoselective rhodium(III)‐catalyzed cascade annulation for the construction of the indolizinone and quinolizinone scaffolds. Diversification of peptidomimetics and oligopeptides is achieved in a rapid and step‐economical manner through the combination of Ugi reaction and microwave‐assisted rhodium(III)‐catalyzed intramolecular annulation via C(sp2)−H activation without installing a directing group. Details of this work can be found in the Communication on pages 4442–4447 (L. Song, G. Tian, A. Blanpain, L. Van Meervelt, E. V. Van der Eycken, Adv. Synth. Catal. 2019, 361, 4442–4447; DOI: 10.1002/adsc.201900550).