Transition-metal-free chemo- and regioselective vinylation of azaallyls

5 years ago

Transition-metal-free chemo- and regioselective vinylation of azaallyls

Ahmet Yeşilçimen, Simon Berritt, Patrick J. Walsh, Eiko Nakamaru-Ogiso, Ana Pascual-Escudero, Marisa C. Kozlowski, Xiaodong Yang, Minyan Li, Georgia Huang, Osvaldo Gutierrez, Javier Adrio

Direct C(sp³)–C(sp²) bond formation under transition-metal-free conditions offers an atom-economical, inexpensive and environmentally benign alternative to traditional transition-metal-catalysed cross-coupling reactions. A new chemo- and regioselective coupling protocol between 3-aryl-substituted-1,1-diphenyl-2-azaallyl derivatives and vinyl bromides has been developed. This is the first transition-metal-free cross-coupling of azaallyls with vinyl bromide electrophiles and delivers allylic amines in excellent yields (up to 99%). This relatively simple and mild protocol offers a direct and practical strategy for the synthesis of high-value allylic amine building blocks that does not require the use of transition metals, special initiators or photoredox catalysts. Radical clock experiments, electron paramagnetic resonance studies and density functional theory calculations point to an unprecedented substrate-dependent coupling mechanism. Furthermore, an electron paramagnetic resonance signal was observed when the N-benzyl benzophenone ketimine was subjected to silylamide base, supporting the formation of radical species upon deprotonation. The unique mechanisms outlined herein could pave the way for new approaches to transition-metal-free C–C bond formations.

Publisher URL: http://dx.doi.org/10.1038/nchem.2760

DOI: 10.1038/nchem.2760