TY - JOUR A1 - Bera, Mrinal K. A1 - Domínguez, Moisés A1 - Hommes, Paul A1 - Reissig, Hans-Ulrich T1 - The Flögel-three-component reaction with dicarboxylic acids – an approach to bis(β-alkoxy-β-ketoenamides) for the synthesis of complex pyridine and pyrimidine derivatives JF - Beilstein Journal of Organic Chemistry PY - 2014/// VL - 10 SP - 394 EP - 404 SN - 1860-5397 DO - 10.3762/bjoc.10.37 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.10.37 KW - alkoxyallenes KW - condensations KW - DFT calculations KW - β-ketoenamides KW - multi-component reactions KW - olefin metathesis KW - pyridines KW - pyrimidines N2 - An extension of the substrate scope of the Flögel-three-component reaction of lithiated alkoxyallenes, nitriles and carboxylic acids is presented. The use of dicarboxylic acids allowed the preparation of symmetrical bis(β-ketoenamides) from simple starting materials in moderate yields. Cyclocondensations of these enamides to 4-hydroxypyridine derivatives or to functionalized pyrimidines efficiently provided symmetrically and unsymmetrically substituted fairly complex (hetero)aromatic compounds containing up to six conjugated aryl and hetaryl groups. In addition, subsequent functionalizations of the obtained heterocycles by palladium-catalyzed couplings or by oxidations are reported. We also describe the simple synthesis of a structurally interesting macrocyclic bispyrimidine derivative incorporating a 17-membered ring, whose configuration was elucidated by DFT calculations and by subsequent reactions. ER -