No abstract

Die basenfreie Anti‐Markownikow‐Addition von sekundären Amiden, Aniliden, Lactamen, Harnstoffderivaten, Bislactamen und Carbamaten an terminale Alkine gelingt erstmalig durch eine rutheniumkatalysierte Reaktion. Zwei komplementäre Protokolle führen jeweils stereoselektiv zu den E‐ oder Z‐Isomeren (siehe Schema; cod=Cycloocta‐1,5‐dien; DMAP=4‐(N,N‐Dimethylamino)pyridin).

Addition reactions O 0060Ru-Catalyzed anti-Markovnikov Addition of Amides to Alkynes: A Regio-and Stereoselective Synthesis of Enamides. -A highly selective anti-Markovnikov addition of secondary amides, anilides, lactams, ureas and carbamates, e.g. (V), (IX) and (XII), to terminal alkynes (II), (VI) and (XV) is developed involving a ruthenium-phosphine complex as catalyst. Thereby, the E/Z-selectivity of the generated double bond is successfully controlled by the nature of catalyst-additive system [cf. (VII)/(VIII) vs. (XVI)/(XVII)]. -(GOOSSEN*, L. J.; RAUHAUS, J. E.; DENG, G.; Angew. Chem., Int. Ed. 44 (2005) 26, 4042-4045; MPI Kohlenforsch., D-45470 Muelheim/Ruhr, Germany; Eng.) -Mischke 43-042