Several ruthenium-catalyzed atom-economic transformations of propargyl alcohols with pyrroles or indoles leading to alkylated, propargylated, or annulated heteroaromatics are reported. The mechanistically distinct reactions are catalyzed by a single ruthenium(0) complex containing a redox-coupled dienone ligand. The mode of activation regarding the propargyl alcohols determines the reaction pathway and depends on the alcohols' substitution pattern. Secondary substrates form alkenyl complexes by a 1,2-hydrogen shift, whereas the transformation of tertiary substrates involves allenylidene intermediates. 1-Vinyl propargyl alcohols are converted by a cascade allylation/cyclization sequence. The environmentally benign processes are of broad scope and allow the selective synthesis of highly functionalized pyrroles and indoles generating water as the only waste product.

Ruthenium‐catalyzed atom‐economic transformations of 1‐vinylpropargyl alcohols with amines leading to highly substituted pyrroles in a one‐pot cascade process are reported. The allylation/cycloisomerization sequence is catalyzed by a single ruthenium(0) complex that contains a redox‐coupled dienone ligand and can be extended by an additional [3,3] rearrangement. The environmentally benign reactions allow the metal‐catalyzed conversion of inexpensive and readily accessible materials to highly functionalized pyrroles with water as the only waste product.

Ruthenium-catalyzed cascade transformations for the synthesis of 2,3-cyclo[3]dendralenes and multicomponent processes based thereon to generate complex polycycles are presented. The combination of allylation-cyclization sequences with diene-transmissive Diels-Alder reactions allows the rapid and selective construction of natural-product-like motifs from easily accessible starting materials in a one-pot process and provides a new method to access potential drug candidates.

Rutheniumkatalysierte Kaskadentransformationen zur Synthese von 2,3‐Cyclo[3]dendralenen und darauf basierende Mehrkomponentenprozesse zum Aufbau komplexer Polycyclen werden vorgestellt. Die Kombination von Allylierungs‐Cyclisierungs‐Sequenzen mit Dien‐transmissiven Diels‐Alder‐Reaktionen ermöglicht den schnellen und selektiven Aufbau naturstoffähnlicher Motive ausgehend von leicht zugänglichen Verbindungen im Eintopfverfahren und eröffnet einen neuen Zugang zu potenziellen Wirkstoffkandidaten.

Ruthenium-Catalyzed Synthesis of Highly Substituted Pyrroles from 1-Vinylpropargyl Alcohols and Amines. -Depending on the substituents on the amine, the initial pyrrole cyclization can be followed by [3,3] rearrangements or Diels-Alder reactions to yield products (X), (XI), (XII), (XIII), or (XV). -(THIES, N.; GERLACH, M.; HAAK*, E.; Eur. J. Org. Chem. 2013, 32, 7354-7365, http://dx.doi.org/10.1002/ejoc.201300803 ; Chem. Inst., Otto-von-Guericke-Univ., D-39106 Magdeburg, Germany; Eng.) -Roessler