New methodologies for incorporation of nitrogen based functional groups onto carbon frameworks

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Abstract

Nitrogen based functional groups are a recurrent motif in most natural products, pharmaceuticals and organic compounds in general. There is therefore a real interest in finding new, efficient and sustainable methodologies to install such functional groups onto carbon skeletons. Herein are presented several methodologies for the functionalisation of a number of substrates by new C−N bond formation. Using photoredox catalysis, the methoxy and di-azidation of styrenes and the benzylic azidation of tolyl substrates was achieved under mild conditions. These processes are notable for using a sustainable and cheap copper-based photoredox catalyst, as opposed to costly metal based complexes. Mechanistic investigations did not provide enough information to propose a definite mechanism for these transformations. Also reported are two strategies for amino arylation reactions. These metal-free functionalisations of internal alkynes, yielding tetra-substituted enaminones, and ketene, affording amides, proceed in good to excellent yields. This goes through a tandem addition/Truce−Smiles rearrangement reaction involving electron deficient sulfonamides under simple, user-friendly conditions.

Keyword(s)

Catalyst; Nitrogen; Photoredox; Rearrangement

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