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Light-Enabled Metal-Free Pinacol Coupling by Hydrazine

Abstract

Efficient carbon-carbon bond formation is of great importance in modern organic synthetic chemistry. The pinacol coupling discovered over a century ago is still one of the efficient coupling reactions to build C-C bond in one step. However, traditional pinacol coupling often requires over stoichiometric amount of active metals as reductants, causing long-lasting metal waste issues and sustainability concerns. A great scientific challenge is to design a metal-free approach to the pinacol coupling reaction. Herein, we describe a light-driven pinacol coupling protocol without use of any metals, instead with N2H4, for the first time, used as a clean non-metallic hydrogen-atom-transfer (HAT) reductant. In this transformation, only traceless non-toxic N2 and H2 gases were produced as by-products with relative broad aromatic ketones scope and good functional group tolerance. A combined experimental and computational investigation of the mechanism suggests that this novel pinacol coupling reaction proceeds via a HAT process between photo-excited ketone and N2H4, instead of the common single-electron-transfer (SET) process for metal reductants.

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Publication details

The article was received on 29 Jul 2019, accepted on 06 Oct 2019 and first published on 11 Oct 2019


Article type: Edge Article
DOI: 10.1039/C9SC03737C
Chem. Sci., 2019, Accepted Manuscript
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Light-Enabled Metal-Free Pinacol Coupling by Hydrazine

    Z. Qiu, H. Pham, J. Li, C. Li, D. Castillo-Pazos, R. Z. Khaliullin and C. Li, Chem. Sci., 2019, Accepted Manuscript , DOI: 10.1039/C9SC03737C

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