Metallvermittelte Mehrkomponentenreaktionen mit Kohlenmonoxid – eine modulare Heterocyclensynthese

Abstract

Heterocyclen am Fließband: Mehrkomponentenreaktionen sind wertvolle Herstellungsverfahren für Substanzbibliotheken insbesondere heterocyclischer Wirkstoffkandidaten. Die Kombination mit metallvermittelten Reaktionen trägt dazu bei, etablierte Methoden zu verbessern, und erleichtert die Entwicklung neuer Strategien. Dieses Highlight präsentiert innovative Einsatzbeispiele mit Kohlenmonoxid zur Synthese diverser Heterocyclen.

A General Approach to Aza‐Heterocycles by Means of Domino Sequences Driven by Hydroformylation

“…[9] All the ligands (PPh 3 (17), xantphos (18), 6-DPPon (19), [23] biphephos (20)) [24,25] produced full conversions to linear or branched aldehydes 11 or 12, with some amounts of the fully reduced adduct 13 (Table 1, entries 1-4). As expected, the bulky diphosphite biphephos favored the formation of the linear aldehyde, whereas xantphos, PPh 3 , or 6-DPPon gave higher amounts of the branched aldehyde.…”

“…The application of hydroformylation in domino processes has been investigated as a strategy to prepare different heterocycles, and several creative applications have been reported. [13][14][15][16][17] Based on our previous experiences in the preparation of aldehydes by hydroformylation, [18][19] we ambitioned to expand the concept of carbonylative-based domino reactions [20] in designing new synthetic routes. In this work, a general approach to aza-heterocycles by domino sequences driven by hydroformylation is disclosed.…”

Molecular Dynamics Simulations of CN− Dynamics and Spectroscopy in Myoglobin

“…The literature witnesses several precedents of domino and/or multicomponent sequences entailing carbonylative steps 5. The following examples represent a non‐exhaustive list: hydroformylation (with syngas)/acetal formation and related sequences,6 radical reactions involving CO,7 multicomponent carbonylative coupling reactions8 such as 1,3‐dipolar cycloadditions involving münchnones,9 carbopalladation/carbonylation sequences,10 and allylic alkylation/Pauson–Khand sequences 11. In most cases the carbonylation step occurs at the end of the sequence, which closes through an intra‐ or intermolecular trapping of a palladium‐carbonyl intermediate.…”