Dynamic kinetic asymmetric amination of branched allylic acetimidates has been applied to the synthesis of 2-alkyl-dihydrobenzoazepin-5-ones. These seven-membered-ring aza ketones are prepared in good yield with high enantiomeric excess by rhodium-catalyzed allylic substitution with 2-amino aryl aldehydes followed by intramolecular olefin hydroacylation of the resulting alkenals. This two-step procedure is amenable to varied functionality and proves useful for the enantioselective preparation of these ring systems.
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Article Synopsis
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- This method exhibits high tolerance for different functional groups and enables the production of acylated cyclopropanes in a controlled, diastereoselective way, utilizing photoinduced decarboxylation.
- The regioselective addition of acyl radicals to the least substituted carbon enhances the method's potential for developing natural products.
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