Modular synthesis of cyclic cis- and trans-1,2-diamine derivativesElectronic supplementary information (ESI) available: Experimental procedures, analytical data of all new compounds. CCDC 973119-973122. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4ob00913d

• Main Authors: Weber, Anna K, Schachtner, Josef, Fichtler, Robert, Leermann, Timo M, Neudörfl, Jörg M, Jacobi von Wangelin, Axel
• Format: Article
• Language: English
• ISSN: 1477-0520; 1477-0539
• DOI: 10.1039/c4ob00913d

Structurally diverse carbocycles with two vicinal nitrogen-substituents were prepared in expedient three-component reactions from simple amines, aldehydes, and nitroalkenes. trans , trans -6-Nitrocyclohex-2-enyl amines were obtained in a one-pot domino reaction involving condensation, tautomerisation, conjugate addition, and nitro-Mannich cyclisation. Upon employment of less nucleophilic carboxamides, a concerted Diels-Alder cycloaddition mechanism operated to give the corresponding cis , trans -nitrocyclohexenyl amides. Both types of substituted carbocycles offer ample opportunities for chemical manipulations at the core and periphery. Ring oxidation with MnO 2 affords substituted nitroarenes. Reduction with Zn/HCl provides access to various trans - and cis -diaminocyclohexenes, respectively, in a straight-forward manner. With enantiopure secondary amines, a two-step synthesis of chiral nitrocyclohexadienes was developed (82-94% ee). Structurally diverse carbocycles with two vicinal nitrogen-substituents were prepared in expedient three-component reactions from simple amines, aldehydes, and nitroalkenes.