RESUMEN
Ruthenium(0) complexes modified by CyJohnPhos or RuPhos catalyze the successive C-C coupling of acetylenic aldehydes with α-ketols to form [4+2] cycloadducts as single diastereomers. This method enables convergent construction of typeâ II polyketide ring systems of the angucycline class.
Asunto(s)
Acetileno/química , Aldehídos/química , Reacción de Cicloadición , Rutenio/química , CatálisisRESUMEN
Upon exposure of 3,4-benzannulated 1,5-diynes (benzo-endiynes) to α-ketols (α-hydroxyketones) in the presence of Ru(0) catalysts derived from Ru3(CO)12 and RuPhos or CyJohnPhos, successive redox-triggered C-C coupling occurs to generate products of [4 + 2] cycloaddition. The proposed catalytic mechanism involves consecutive alkyne-carbonyl oxidative couplings to form transient oxaruthanacycles that suffer α-ketol mediated transfer hydrogenolysis. This process provides a new, convergent means of assembling Type II polyketide substructures.
Asunto(s)
Alquinos/química , Cetonas/química , Compuestos Organometálicos/química , Policétidos/síntesis química , Rutenio/química , Catálisis , Ciclización , Hidrogenación , Estructura Molecular , Policétidos/químicaRESUMEN
Catalytic enantioselective methods for the preparation of chiral azaarene-containing compounds are of high value. By combining the utility of copper hydride catalysis with the ability of CâN-containing azaarenes to activate adjacent alkenes toward nucleophilic additions, the enantioselective reductive coupling of alkenylazaarenes with ketones has been developed. The process is tolerant of a wide variety of azaarenes and ketones, and provides aromatic heterocycles bearing tertiary-alcohol-containing side chains with high levels of diastereo- and enantioselection.
Asunto(s)
Alquenos/química , Compuestos Aza/química , Cobre/química , Hidrocarburos Aromáticos/química , Cetonas/química , Catálisis , Oxidación-Reducción , EstereoisomerismoRESUMEN
The versatility of chiral copper hydride catalysis has been demonstrated through development of highly enantioselective 1,4-reductions of 2-alkenylheteroarenes, substrates that have been rarely considered for asymmetric conjugate addition reactions. Both azoles and azines serve as efficient activating groups for this process.