A palladium catalyzed stereo-convergent aminocarbonylation of 1,3-dienes with nitroarenes: synthesis of (E,E)-dienamides

Abstract

A palladium catalyzed stereo-convergent aminocarbonylation of 1,3-dienes with nitroarenes has been developed. The reaction proceeds in a highly stereoconvergent manner, the reaction of mixtrues of E/Z isomers of 1,3-dienes reacted...

Use of Formic Acid as a CO Surrogate for the Reduction of Nitroarenes in the Presence of Dienes: A Two‐Step Synthesis of N‐Arylpyrroles via 1,2‐Oxazines

“…Employing 1‐phenyl‐1,3‐butadiene ( 2 c ) as the diene, only the proximal isomer was obtained, again in accordance with the literature for the same [5b] or related compounds [27] . It should be noted that nitroarenes and dienes have been recently reported to afford amides when a different catalytic system (Pd(PPh 3 ) 4 with Mo(CO) 6 as a CO surrogate) was employed [35] . In this system, the formation of free nitrosoarenes as intermediates was excluded.…”

“…[27] It should be noted that nitroarenes and dienes have been recently reported to afford amides when a different catalytic system (Pd(PPh 3 ) 4 with Mo(CO) 6 as a CO surrogate) was employed. [35] In this system, the formation of free nitrosoarenes as intermediates was excluded.…”

Palladium(0) π-Lewis Base Catalysis: Concept and Development

“…As outlined in Scheme d, the α-carbonyl group of α-ketoamides 14 could be attacked by 1,3-dienes in the presence of Pd(0) and bifunctional ligand L3 , thus furnishing enantioenriched 3,5- cis -difunctionalized γ-lactams 15 after subsequent intramolecular allylic amination . In addition, isocyanatoarenes were found to be suitable electrophilic partners to access dienamide products …”

Access to Amides and Lactams via Pyridotriazole as a Transformable Directing Group

“…Amide and lactam scaffolds are a class of substantial motifs frequently found in pharmaceuticals and naturally occurring molecules like imatinib, lenalidomide, and elmenol H. − A wide range of approaches to constructing such indispensable amide bonds have been developed, ranging from conventional acylation of amines mediated by amide coupling agents , to modern strategies such as catalytic direct amidation , or visible light irradiation. , Among these studies, transition-metal-catalyzed C–H activation stands out as a simpler synthetic route for direct amidation of unactivated C–H bonds. − Many transition-metal-catalyzed C–H functionalization methods require directing groups (DGs), − especially transformable DGs, to enhance the regioselectivity and practicality. − By the DG-assisted C–H activation strategy, selectively installing nitrogen-based functional groups (FGs) into molecules via the direct addition of C–H bonds to unsaturated polar C–N π-bonds represents the most powerful and economical method for rapid amide and lactam synthesis. − We envisioned isocyanates to be particularly useful. As useful carbon synthons in organic synthesis, isocyanates have been extensively implemented in the construction of C–C bond formation for forging amides. − Hence, employing isocyanates as FGs would be a more straightforward approach to the synthesis of amides.…”