The chemoselective photoreduction of aldehydes in the presence of ketones was achieved using triethanolamine (TEOA) as sacrificial electron donor, proflavine (PF) as photocatalyst and [Cp*Rh(iii)(bpy)Cl]Cl (Rhcat) as mediator. The reducing agent, which reacts with the carbonyl group was found to be [Cp*Rh(iii)(bpy)H]Cl (Rh(iii)-H). Contrary to formate-based reduction, its slow photochemical in situ generation enables to kinetically distinguish aldehydes from ketones. The inherent reactivity difference of the carbonyl compounds is transferred by the method into synthetically useful reaction selectivities. The substrate scope is broad with excellent yields. A detailed study of the reaction mechanism reveals that the photoreduction of the PF triplet and the subsequent reduction of the Rhcat leading to Rh(iii)-H represents the major reaction pathway, which is highly oxygen sensitive. The oxidative quenching of the PF singlet state by Rhcat is a competing mechanism, which prevails in non-degassed systems.

Department of Chemistry Faculty of Science Masaryk University Kamenice 5 62500 Brno Czech Republic

Institute of Organic Chemistry University of Regensburg D 93040 Regensburg Germany Email

Research Centre for Toxic Compounds in the Environment Faculty of Science Masaryk University Kamenice 5 62500 Brno Czech Republic

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Tolstikov G. A., Odinokov V. N., Galeeva R. I., Bakeeva R. S., Akhunova V. R. Tetrahedron Lett. 1979;20:4851–4854.

Hutchins R. O., Kandasamy D. J. Am. Chem. Soc. 1973;95:6131–6133.

Ward D. E., Rhee C. K. Synth. Commun. 1988;18:1927–1933.

Ward D. E., Rhee C. K. Can. J. Chem. 1989;67:1206–1211.

Maki Y., Kikuchi K., Sugiyama H., Seto S. Tetrahedron Lett. 1977;18:263–264.

Adams C. Synth. Commun. 1984;14:1349–1353.

Zeynizadeh B., Shirini F. J. Chem. Res. 2003;2003:334–339.

Tanemura K., Suzuki T., Nishida Y., Satsumabayashi K., Horaguchi T. Synth. Commun. 2005;35:867–872.

Chandrasekhar S., Shrinidhi A. Synth. Commun. 2014;44:2051–2056.

Raber D. J., Guida W. C., Shoenberger D. C. Tetrahedron Lett. 1981;22:5107–5110.

Gribble G. W., Ferguson D. C. J. Chem. Soc., Chem. Commun. 1975:535–536.

Nutaitis C. F., Gribble G. W. Tetrahedron Lett. 1983;24:4287–4290.

Kuroiwa Y., Matsumura S., Toshima K. Synlett. 2008;2008:2523–2525.

Casey C. P., Strotman N. A., Beetner S. E., Johnson J. B., Priebe D. C., Guzei I. A. Organometallics. 2006;25:1236–1244.

Zhang M., Rouch W. D., McCulla R. D. Eur. J. Org. Chem. 2012;2012:6187–6196.

Nam D. H., Park C. B. ChemBioChem. 2012;13:1278–1282. PubMed

Armstrong R. W., Panzer N. M. J. Am. Chem. Soc. 1972;94:7650–7653. PubMed

Krasna A. I. Photochem. Photobiol. 1979;29:267–276.

Youinou M. T., Ziessel R. J. Organomet. Chem. 1989;363:197–208.

Hollmann F., Schmid A., Steckhan E. Angew. Chem., Int. Ed. 2001;40:169–171. PubMed

Lo H. C., Buriez O., Kerr J. B., Fish R. H. Angew. Chem., Int. Ed. 1999;38:1429–1432. PubMed

Leiva C., Lo H. C., Fish R. H. J. Organomet. Chem. 2010;695:145–150.

Himeda Y., Onozawa-Komatsuzaki N., Sugihara H., Arakawa H., Kasuga K. J. Mol. Catal. A: Chem. 2003;195:95–100.

Kölle U., Grätzel M. Angew. Chem., Int. Ed. Engl. 1987;99:572–574.

Menche D., Hassfeld J., Li J., Menche G., Ritter A., Rudolph S. Org. Lett. 2006;8:741–744. PubMed

Haugen G. R., Melhuish W. H. Trans. Faraday Soc. 1964;60:386.

Mataga N., Kaifu Y., Koizumi M. Bull. Chem. Soc. Jpn. 1956;29:373–379.

Parker C. A., Joyce T. A. Photochem. Photobiol. 1973;18:467–474. PubMed

Lee W. E., Galley W. C. Biophys. J. 1988;54:627–635. PubMed PMC

Kurz P., Probst B., Spingler B., Alberto R. Eur. J. Inorg. Chem. 2006;2006:2966–2974.

Pileni M. P., Grätzel M. J. Phys. Chem. 1980;84:2402–2406.

Chakraborty B., Basu S. Chem. Phys. Lett. 2009;477:382–387.

Steckhan E., Herrmann S., Ruppert R., Dietz E., Frede M., Spika E. Organometallics. 1991;10:1568–1577.

Lee S. H., Nam D. H., Kim J. H., Baeg J.-O., Park C. B. ChemBioChem. 2009;10:1621–1624. PubMed

Lee S. H., Nam D. H., Park C. B. Adv. Synth. Catal. 2009;351:2589–2594.

Lo H. C., Leiva C., Buriez O., Kerr J. B., Olmstead M. M., Fish R. H. Inorg. Chem. 2001;40:6705–6716. PubMed

Solar S., Solar W., Getoff N. Z. Naturforsch., A: Phys. Sci. 1982;37:1077–1082.

Oster G., Bellin J. S., Kimball R. W., Schrader M. E. J. Am. Chem. Soc. 1959;81:5095–5099.

Hussein B. H. M. and Goez M., Ph.D. Dissertation, Universität Halle-Wittenberg, Germany, 2005.

Kalyanasundaram K., Dung D. J. Phys. Chem. 1980;84:2551–2556.

Lv H., Guo W., Wu K., Chen Z., Bacsa J., Musaev D. G., Geletii Y. V., Lauinger S. M., Lian T., Hill C. L. J. Am. Chem. Soc. 2014;136:14015–14018. PubMed

Barrett S. M., Pitman C. L., Walden A. G., Miller A. J. M. J. Am. Chem. Soc. 2014;136:14718–14721. PubMed

Structural elaboration of dicyanopyrazine: towards push-pull molecules with tailored photoredox activity