Organocatalytic asymmetric transformation of common aromatic heterocycles via in situ formation of highly reactive dearomatized ortho-quinodimethane diene species and subsequent [4+2] cycloaddition with suitable dienophiles has become a powerful tool to enter cyclohexane-fused heterocycles. Most of these reactions were previously applied to benzofused heterocycles or poorly aromatic rings. Herein, we disclose how previously intractable aromatic imidazole rings, equipped with removable methylidene malononitrile activating handle, could be involved as competent cycloaddends with beta-aryl enals in efficient eliminative [4+2] cycloadditions under mild organocatalytic conditions. This method allowed the efficient and direct preparation of scantly represented 6,7- dihydrobenzo[d]imidazoles with optimal enantio- and regioselectivities. Post-cycloaddition chemical editing provided imidazole-based ring systems with diverse oxidation state and functional groups.

Turning the Imidazole Core into Three‐Dimensional Ring Systems: Mild Organocatalytic Entry to Enantiopure 6,7‐Dihydrobenzimidazoles / Marcantonio, Enrico; Guazzetti, Debora; Bugatti, Kelly; Battistini, Lucia; Sartori, Andrea; Pelosi, Giorgio; Curti, Claudio; Zanardi, Franca. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - e202301200:(2023). [10.1002/chem.202301200]

Turning the Imidazole Core into Three‐Dimensional Ring Systems: Mild Organocatalytic Entry to Enantiopure 6,7‐Dihydrobenzimidazoles

Marcantonio, Enrico;Guazzetti, Debora;Bugatti, Kelly;Battistini, Lucia;Sartori, Andrea;Pelosi, Giorgio;Curti, Claudio
;
Zanardi, Franca
2023-01-01

Abstract

Organocatalytic asymmetric transformation of common aromatic heterocycles via in situ formation of highly reactive dearomatized ortho-quinodimethane diene species and subsequent [4+2] cycloaddition with suitable dienophiles has become a powerful tool to enter cyclohexane-fused heterocycles. Most of these reactions were previously applied to benzofused heterocycles or poorly aromatic rings. Herein, we disclose how previously intractable aromatic imidazole rings, equipped with removable methylidene malononitrile activating handle, could be involved as competent cycloaddends with beta-aryl enals in efficient eliminative [4+2] cycloadditions under mild organocatalytic conditions. This method allowed the efficient and direct preparation of scantly represented 6,7- dihydrobenzo[d]imidazoles with optimal enantio- and regioselectivities. Post-cycloaddition chemical editing provided imidazole-based ring systems with diverse oxidation state and functional groups.
2023
Turning the Imidazole Core into Three‐Dimensional Ring Systems: Mild Organocatalytic Entry to Enantiopure 6,7‐Dihydrobenzimidazoles / Marcantonio, Enrico; Guazzetti, Debora; Bugatti, Kelly; Battistini, Lucia; Sartori, Andrea; Pelosi, Giorgio; Curti, Claudio; Zanardi, Franca. - In: CHEMISTRY-A EUROPEAN JOURNAL. - ISSN 0947-6539. - e202301200:(2023). [10.1002/chem.202301200]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11381/2945653
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