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Spatiotemporal Control of Amide Radicals During Photocatalysis

preprint
submitted on 27.03.2020 and posted on 30.03.2020 by Shogo Mori, Takahiro Aoki, Kaliyamoorthy Selvam, Shunichi Fukuzumi, Jieun Jung, Susumu Saito
Despite the continuing popularity of radical reactions in organic synthesis, much remains to be explored in this area. Herein, we describe how spatiotemporal control can be exerted over the formation and reactivity of divergent exchangeable formamide radicals using nickel complexes with a semiconductor material (TiO2) under irradiation from near-UV–Vis light. Depending on the bipyridine ligand used and the quantity of the nickel complex that is hybridized on or nonhydridized over the TiO2 surface, these radicals selectively undergo substitution reactions at the carbon center of carbon–bromine bonds that proceed via three different pathways. As the scalable production of formamides from CO2 does not produce salt waste, these methods could add a new dimension to the search for carbon neutrality through the indirect incorporation of CO2 into organic frameworks.

Funding

Asahi Glass Foundation

Grant-in-aid for Scientific Research on Innovative Areas (18H04247)

JSPS grant for Early-Career Scientists (18K14241)

JSPS fellowship for foreign researchers (P16040)

GTR, Nagoya University

History

Email Address of Submitting Author

saito.susumu@f.mbox.nagoya-u.ac.jp

Institution

Nagoya University

Country

Japan

ORCID For Submitting Author

0000-0003-0749-2020

Declaration of Conflict of Interest

The authors declare no competing financial interest.

Version Notes

1st version

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