We developed a silver‐catalyzed strategy for the generation of sulfonyl radicals from sulfonamides derived from α‐amino acids. The reaction proceeded via a decarboxylation, N–S bond cleavage and radical cyclization sequence and allows the difunctionalization of alkynes and the synthesis of 3‐sulfonylated coumarins. The reaction tolerated a broad scope of substrates and functional groups and could be extended to the synthesis of oxindoles and an isoquinolinedione by the capturing of the sulfonyl radical with an alkene moiety. Moreover, the proposed mechanism was supported experimentally and by DFT calculations.

α-Aminoalkylation of N-arylacrylamides with amino acid derivatives was achieved by silver-catalysis in moderate to high yields. The reaction provides an efficient strategy for the synthesis of functionalized oxindoles, and is suitable for a wide range of N-arylacrylamides and amino acids, both of which are inexpensive and readily available. The oxindoles obtained were readily transformed into densely functionalized pyrroloindolines by deprotection and cyclization in one pot.

The Front Cover shows a fisherman using bait to catch fish from a pond. The mackerel and red snapper in the pond eat a part of the bait, and then they are pulled by the fisherman and given to the boy. The fisherman symbolizes a chemist using cheap and readily available α‐amino acid sulfonamides that are easy to prepare from α‐amino acids. The pond symbolizes a reaction flask, where the fish eat a part of the amino acid, SO2R radical. The pulling up of the fish symbolizes isolation of the synthesized products More information can be found in the https://doi.org/10.1002/ejoc.201800901

Amino acids are readily available, stable, structurally variable, and inexpensive, making them attractive starting materials for synthesis of complex organic compounds. As shown on the cover picture, α‐amino acids were used as precursors for the concise synthesis of oxindoles using silver‐catalyzed decarboxylative radical addition to N‐aryl acrylamides. The α‐aminoalkylation tolerates a broad scope of functional groups often used in organic synthesis. Moreover, the synthesized oxindoles were readily transformed into densely functionalized pyrroloindolines by deprotection and cyclization. More information can be found in the Communication by Kyalo Stephen Kanyiva et al. on page 496 in Issue 5, 2018 (DOI:10.1002/asia.201701739).