Cross-conjugated vinylogous annulation of π-CF3-allyl Pd-complexes with 4-methyl-3-trifluoroacetyl-quinolones.

Herein, we disclose the hitherto unknown cross-conjugated vinylogous annulation of π-CF3-allyl Pd complexes with 4-methyl-3-trifluoroacetyl-quinolones to access phenanthridones. The CF3 group in the Pd-π-allyl complex is key for exclusive γ-regioselectivity and further annulation. The solvent switch orchestrates the dihydro-phenanthridones (CH3CN) and hydroxy-phenanthridones (DMF) in good yields, and also showed excellent optoelectronic properties.

3-Trifluoroacetyl-quinolin-2(1H)-ones as Carbonyl and Acid Surrogates in the Passerini-/Ugi-Type Reaction.

Herein, we report tailored 3-trifluoroacetyl-quinolin-2(1H)-ones (1) as carbonyl and acid surrogates in Passerini- and Ugi-type reactions for the synthesis of α-trifluoromethyl-α-hydroxy carboxamides (4) and α-trifluoromethyl α-amino acids (6) in high yields, respectively. The reaction proceeds under mild reaction conditions via an exocyclic carboximidate intermediate (3). The amide group in compound 1 acts as an acid component as well as a reversible oxygen nucleophile to facilitate the reaction.