| Abstract: | A catalyst‐free, environmentally benign three‐component vinylogous Mukaiyama–Mannich reaction of pyrrole‐based silyl dienolates is presented, which works effectively in both aqueous and solvent‐free environments. Both lipophilic and hydrophilic aldehyde candidates are suitable substrates, allowing access to a rich repertoire of unsaturated vicinal aminolactam structures with virtually complete γ‐site selectivity and moderate to good anti‐diastereoselectivity. The utility of this technology is highlighted by protecting group‐free synthesis of densely hydroxylated, sugar‐related lactam frameworks. The role of water as an indispensable H‐bonding reaction propeller is demonstrated. |
