Palladium- and Copper-Catalyzed Synthesis of Medium- and Large-Sized Ring-Fused Dihydroazaphenanthrenes and 1,4-Benzodiazepine-2,5-diones. Control of Reaction Pathway by Metal-Switching
Methods for the synthesis of dihydroazaphenanthrene fused to macrocycles I [X = CH2, O, Y = (CH2)m, m = 1,2,4,6, n = 1,2] and medium-ring heterocycles II (R1 = H, Me, CH2Ph, etc., R2 = Me, n-Bu, CH2Ph, etc.) as well as 1,4-benzodiazepine-2,5-diones, e.g. III, are developed. A distinctly different catalytic property of palladium and copper catalysts was uncovered that leads to the development of a divergent synthesis of two different heterocyclic scaffolds from the same starting materials, simply by metal-switching. Thus, starting from linear amide IV, palladium acetate triggers a domino intramol. N-arylation/C-H activation/aryl-aryl bond-forming process to provide II, while copper iodide promotes only the intramol. N-arylation reaction leading to the 1,4-benzodiazepine-2,5-diones. In combination with the Ugi multicomponent reaction (Ugi-4CR) for the prepn. of the linear amides, a two-step synthesis of either the 5,6-dihydro-8H-5,7a-diazacyclohepta[jk]phenanthrene-4,7-dione (4) or 1,4-benzodiazepine-2,5-diones (5), by appropriate choice of metal catalyst, is subsequently developed from very simple starting materials. [on SciFinder (R)]
2004
126
44
14475
14484
CAN 142:38222
28-21
Heterocyclic Compounds (More Than One Hetero Atom)
Institut de Chimie des Substances Naturelles,CNRS,Gif-sur-Yvette,Fr.
Journal
written in English.
66-71-7 (1,10-Phenanthroline); 107-97-1 (Sarcosine); 108-00-9 (N,N-Dimethylethylenediamine); 123-54-6 (2,4-Pentanedione); 142-71-2 (Copper(II) acetate); 527-72-0 (2-Thiophenecarboxylic acid); 998-40-3 (Tributylphosphine); 1121-22-8 (trans-1,2-Cyclohexanediamine); 1317-38-0 (Copper(II) oxide); 3375-31-3 (Palladium(II) acetate); 7440-50-8 (Copper); 7447-39-4 (Copper(II) chloride); 7681-65-4 (Copper(I) iodide); 7758-89-6 (Copper(I) chloride); 7758-98-7 (Copper sulfate); 12150-46-8 (Dppf); 14221-01-3 (Tetrakis(triphenylphosphine)palladium); 32005-36-0; 68986-76-5 (Copper(I) thiophene-2-carboxylate); 72287-26-4 (PdCl2(dppf); 98327-87-8 (BINAP) Role: CAT (Catalyst use), USES (Uses) (prepn. of linear alpha -acetamido amides via Ugi 4-component coupling and their palladium- and copper-catalyzed cyclization to give fused azaphenanthrenes and benzodiazepinediones); 78-84-2 (Isobutyraldehyde); 88-67-5 (2-Iodobenzoic acid); 100-46-9 (Benzylamine); 109-73-9 (n-Butylamine); 109-76-2 (1,3-Propanediamine); 110-60-1 (1,4-Butanediamine); 111-71-7 (Heptanal); 122-78-1 (Phenylacetaldehyde); 124-09-4 (1,6-Hexanediamine); 373-44-4 (1,8-Octanediamine); 590-86-3; 600-21-5; 609-67-6; 2566-30-5 (N-Methylphenylalanine); 2566-32-7; 2752-17-2; 3060-46-6 (N-Methylleucine); 15761-39-4; 18545-16-9; 20781-20-8 (2,4-Dimethoxybenzyl amine); 37784-17-1; 39687-95-1; 39959-51-8 (2-Iodobenzyl amine); 52548-14-8 (2-Iodo-5-methylbenzoic acid); 63212-42-0 (3-Iodo-2-naphthalenecarboxylic acid); 78375-48-1; 98648-05-6; 588708-17-2; 807355-02-8 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. of linear alpha -acetamido amides via Ugi 4-component coupling and their palladium- and copper-catalyzed cyclization to give fused azaphenanthrenes and benzodiazepinediones); 638195-20-7P; 638195-26-3P; 638195-28-5P; 638195-29-6P; 638195-31-0P; 638195-38-7P; 638195-39-8P; 638195-40-1P; 638195-41-2P; 638195-42-3P; 807354-77-4P; 807354-88-7P; 807354-89-8P; 807354-90-1P; 807354-91-2P; 807354-92-3P; 807354-93-4P; 807354-94-5P; 807354-95-6P; 807354-96-7P; 807354-97-8P; 807354-98-9P; 807354-99-0P; 807355-00-6P; 807355-01-7P; 807355-09-5P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of linear alpha -acetamido amides via Ugi 4-component coupling and their palladium- and copper-catalyzed cyclization to give fused azaphenanthrenes and benzodiazepinediones); 638195-21-8P; 638195-22-9P; 638195-23-0P; 638195-24-1P; 638195-25-2P; 638195-27-4P; 638195-33-2P; 638195-34-3P; 638195-36-5P; 638195-43-4P; 807354-76-3P; 807354-78-5P; 807354-79-6P; 807354-80-9P; 807354-81-0P; 807354-82-1P; 807354-83-2P; 807354-84-3P; 807354-85-4P; 807354-86-5P; 807354-87-6P; 807355-03-9P; 807355-04-0P; 807355-05-1P; 807355-07-3P; 807355-08-4P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of linear alpha -acetamido amides via Ugi 4-component coupling and their palladium- and copper-catalyzed cyclization to give fused azaphenanthrenes and benzodiazepinediones)
REVIEWED
OTHER