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  • Perspective
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Catalytic acceptorless dehydrogenative coupling mediated by photoinduced hydrogen-atom transfer

Nature Synthesis volume 2, pages 209–216 (2023)Cite this article

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Abstract

Acceptorless dehydrogenative cross-coupling between two carbon–hydrogen (C–H) bonds has garnered increasing attention in synthetic chemistry. Cross-coupling of this type does not require the use of functionalized reactive reagents such as organic halides and organometallics. In addition, acceptorless dehydrogenation can proceed without external oxidants, releasing molecular hydrogen as the sole by-product. These features enable target molecules to be accessed with fewer synthetic steps and reduced waste. For the development of dehydrogenative cross-coupling reactions, viable methodologies for the cleavage of C–H bonds are crucial. Hydrogen-atom transfer (HAT) catalysis has significant potential because a diverse range of hydrocarbons can be subjected to HAT. This Perspective describes the use of photoinduced HAT catalysis in acceptorless dehydrogenative reactions, with the aim of providing an opportunity to consider the future prospects of this methodology.

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Fig. 1: Hybrid catalysis using a cobaloxime and TBADT.
Fig. 2: ADC reactions based on the use of heteroatom-centred radicals.
Fig. 3: ADC reactions based on the use of an iridium-based photosensitizer and organic molecular HAT catalyst46.
Fig. 4: ADC reactions using an iridium-based photosensitizer and a nickel catalyst47.

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Acknowledgements

This report was prepared as an account of work supported by JSPS KAKENHI Grant Number JP17H06446 in Hybrid Catalysis for Enabling Molecular Synthesis on Demand and JP21H01930.

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  1. Institute of Transformative Bio-Molecules (WPI-ITbM), and Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan

    Kohsuke Ohmatsu & Takashi Ooi

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K.O. and T.O. contributed to discussions and wrote the manuscript.

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Correspondence to Takashi Ooi.

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Nature Synthesis thanks Chao-Jun Li and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Thomas West, in collaboration with the Nature Synthesis team.

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Ohmatsu, K., Ooi, T. Catalytic acceptorless dehydrogenative coupling mediated by photoinduced hydrogen-atom transfer. Nat. Synth 2, 209–216 (2023). https://doi.org/10.1038/s44160-022-00195-1

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