Neue Methoden in der radikalischen Heterocyclensynthese (English shop)

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The work presented here deals with the generation and synthetic utility of alkoxyamidyl radicals. While the common methods for generating amidyl radicals cannot be transferred to their alkoxy derivatives, the class of N-centered radicals newly developed in this work can be successfully formed by an oxidative route through reaction with IBX (2-iodoxybenzoic acid) and employed in cyclization reactions. The resulting heterocycles can be converted, following N–O bond cleavage, into preparatively valuable amino alcohols.

In a second project, a method for PRE-controlled quinoline synthesis is presented. Through thermolysis of readily accessible TEMPO-derived alkoxyamines as C-radical precursors in the presence of an aryl isonitrile, quinoline derivatives with complex substitution patterns can be prepared in [4+1] annulations without the use of toxic organotin compounds. By employing microwave irradiation, the reaction times can be reduced from 3 days to 30 minutes.