RSC Harrison-Meldola Memorial Prize Lecture - Photoinduced Assembly of C-N Bonds
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Photoinduced Assembly of C -N Bonds
Dr Daniele Leonori
School of Chemistry, University of Manchester, Manchester M13 9PL, UK
Nitrogen -containing compounds are a privileged class of molecules, which have
applications in medicines, agrochemicals, dyes and materials. This relevance makes
the construction of C –N bonds an extremely active area of research.
Nitrogen -radicals are versa tile synthetic intermediates that can engage in a broad
range of chemical reactions. 1 However, the difficulties associated with their generation
have somewhat thwarted their use in synthetic chemistry.
Development of Photoinduced Radical -Transposition Reactions
We have developed a class of easy -to -make oximes and hyroxy -amides that upon
photoredox oxidation enable access to iminyl and amidyl radicals. 2,3 These species
have been used in radical transposition reactions for the site -selective
functionaliza tion of unactivated sp 3-carbons. These strategies have been applied to
the deconstruction –functionalization of complex steroids (radical ring -opening) 2 and to
the preparation of unnatural aminoacids (1,5 -HAT) .3
Development of Photoinduced Aromatic C –H Ami nation Reactions
Aminated aromatics are a widespread motif in high -value products. In general, these
structures are assemble d by Pd or Cu -catalysed cross -couplings between aryl
halides/organoboron and amines. We have developed an umpolung approach where
electrophilic amidyl and aminyl radicals are generated by photoredox reduction of
electron poor N-aryloxy -amides and -amines. 4,5 These radical specie s undergo highly
selective addition to a broad range of electron rich aromatics thus enabling direct C –
1. Review: S. Z. Zard Chem. Soc. Rev. 2008 , 37 , 1603.
2. Angew. Chem. Int. Ed. 2018 , 57 , 744.
3. Angew. Chem. Int. Ed. 2018 , 57 , 12495.
4. J. Am. Chem. Soc. 2016 , 138 , 8092.
5. Angew. Chem. Int. Ed. 2017 , 56 , 14948. Download PDF
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