Divergent Sequential Reactions of β‐(2‐Aminophenyl)‐α,β‐ynones with Malonyl Chloride

Abstract

A viable one-pot synthesis of challenging 4H- [3,4-c]quinolone-4,5(6H)-diones by the reaction of β-(2-aminophenyl)-α,β-ynones with ethyl malonyl chloride is described. Their further elaboration in the presence of an excess of 40 % methyl amine aqueous solution in EtOH gives the benzo[c][2,7]naphthyridine-4,5(3H,6H)-diones of pharmacological interest in high yields.The product selectivity control of the divergent sequential condensation/C-annulation/intramolecular transesterification vs condensation/O-annulation/ring opening reactions of β-(2-aminophenyl)-α,β-ynones with malonyl chloride under metal free conditions has been addressed.

On Route to Diverse Nitrogen‐Bridged Polyhetero‐cycles with an N(acyl), N(aryl)‐acetal Core

“…Pleasantly, under standard electrochemical conditions (method A), anilines with ortho‐α,β‐ynones 2 h – 2 l [26] performed quite well, directly providing the corresponding tetracyclic keto‐enamides 5 , as a single diastereoisomer, via tandem addition/cyclization/rearrangement and subsequent aza‐Michael reaction to the α,β‐akynoyl moiety. Interestingly, EWG and ERG substituents on the aromatic ring directly bonded to the carbonyl affect both the final yield in isolated 5 and the tetracyclic/acyclic isoindolinones ratio.…”

Electrocatalytic Hydrogen Evolution Reaction Enabling Cyanation of Electron‐poor Carbons with Acetone Cyanohydrin

“…Starting materials 1 a , 1 m – q , and 3 j – k are commercially available and were used without any further purification. Starting materials 1 b – l [17a] 1 r , [17b] 1 s [17c] , 1 t [17d] and 3 a – i [18] were prepared as reported in the literature.…”