Quinones constitute an important class of reactive synthons being widely used in organic synthesis with increasing reports on their enantioselective transformations. However, most of them are restrained to stable and isolatable 1,4-quinones. Labile quinone derivatives such as quinone imines, <i>ortho</i>-quinones are rarely applied due to their strong propensity to hydrolysis and dimerization. Therefore, new strategies to control these labile molecules for selective reactions toward important molecular frameworks are in high demand. Inspired by biosynthetic reactions of quinones in nature, herein we report a biomimetic relay catalysis strategy to prepare labile quinone intermediates in situ via chemoselective oxidation from readily available phenol precursors under mild and sustainable conditions. Moreover, we are able to harness them for various succeeding reactions with excellent chemoselectivity, regioselectivity and stereoselectivity, as seen in [3+2], [4+2], allylic amination and 1,2-diamination. This strategy allows access to broader substrate scope, higher step and atom economy in comparison to conventional quinone reactions, thus enriching the chemistry of quinones particularly for constructing complex molecular frameworks and value-added compounds.

Biomimetic relay catalytic transformation of labile quinones

ACS Spring Meeting 2021

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