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Ground-state dioxygen undergoes metal-free [3 + 2]-annulations with allenes and nitrosoarenes under ambient conditions

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Abstract

The cycloadditions of molecular dioxygen with neutral π-bond motifs rely heavily on singlet-state 1O2, whereas ground state 3O2 is chemically inactive. Here we report novel [3 + 2]-annulations among ground-state 3O2 (1 bar), allenes, and nitrosoarenes at low temperatures, efficiently yielding dioxygen-containing oxacycles. With less hindered 1-arylallene derivatives, these dioxygen species undergo skeletal rearrangement to 3-hydroxy-1-ketonyl-2-imine oxides. These cycloadditions represent valuable one-pot O,N,O-trifunctionalizations of allenes. Our EPR experiments confirm the presence of 1,4-diradical intermediates from an allene/nitrosoarene mixture, which manifest the hidden diradical properties of nitrosoarenes.

Graphical abstract: Ground-state dioxygen undergoes metal-free [3 + 2]-annulations with allenes and nitrosoarenes under ambient conditions

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Publication details

The article was received on 20 Apr 2017, accepted on 20 May 2017 and first published on 24 May 2017


Article type: Edge Article
DOI: 10.1039/C7SC01770G
Citation: Chem. Sci., 2017, Advance Article
  • Open access: Creative Commons BY license
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    Ground-state dioxygen undergoes metal-free [3 + 2]-annulations with allenes and nitrosoarenes under ambient conditions

    J. Liu, M. Skaria, P. Sharma, Y. Chiang and R. Liu, Chem. Sci., 2017, Advance Article , DOI: 10.1039/C7SC01770G

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