Volume 2, Issue 3, Pages 383-392 (March 2017) Catalytic Dehydrogenative C–H Imidation of Arenes Enabled by Photo-generated Hole Donation to Sulfonimide  Eri Ito, Tomohiro Fukushima, Takahiro Kawakami, Kei Murakami, Kenichiro Itami  Chem  Volume 2, Issue 3, Pages 383-392 (March 2017) DOI: 10.1016/j.chempr.2017.02.006 Copyright © 2017 Elsevier Inc. Terms and Conditions

Chem 2017 2, 383-392DOI: (10.1016/j.chempr.2017.02.006) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 1 Overview of This Work (A) Nitrogen sources in aromatic C–H amination and imidation reactions. (B) Equimolar, dehydrogenative imidation of arenes (this work). Chem 2017 2, 383-392DOI: (10.1016/j.chempr.2017.02.006) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 2 Ru-Catalyzed Dehydrogenative C–H Imidation of Naphthalene under Blue LED Light Chem 2017 2, 383-392DOI: (10.1016/j.chempr.2017.02.006) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 3 Scope of Sulfonimide Reactivity For 2h: 1h (1.5 equiv), [Ru(bpy)3]Cl2·6H2O (2.5 mol %), IBB (3.0 equiv), 24 hr. Chem 2017 2, 383-392DOI: (10.1016/j.chempr.2017.02.006) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 4 Scope of the Aromatic C–H Imidation For 3b, 3e, 3f, and 3l–3q: 1a (1.5 equiv), [Ru(bpy)3]Cl2·6H2O (2.5 mol %), IBB (3.0 equiv), 24 hr. For 3g: 1a (1.5 equiv), [Ru(bpy)3]Cl2·6H2O (5.0 mol %), IBB (3.0 equiv), 24 hr. For 3s and 3t: 1a (5.0 equiv), [Ru(bpy)3]Cl2·6H2O (2.5 mol %), PhI(OAc)2 (5.0 equiv), 12 hr. Chem 2017 2, 383-392DOI: (10.1016/j.chempr.2017.02.006) Copyright © 2017 Elsevier Inc. Terms and Conditions

Figure 5 Mechanistic Consideration (A) Cyclic voltammograms of 5 mM Ru(bpy)3Cl2·6H2O (black line), + 1 mM 1a (blue line), and + 5 mM 1a (red line) in 50 mM TBAPF6/DCE under Ar (0.1 V/s). (B) Plausible reaction mechanism. Chem 2017 2, 383-392DOI: (10.1016/j.chempr.2017.02.006) Copyright © 2017 Elsevier Inc. Terms and Conditions

Scheme 1 Sequence of C–H Imidation, Desulfonylation, and N–H Arylation in the Synthesis of a Sulfonamide Chem 2017 2, 383-392DOI: (10.1016/j.chempr.2017.02.006) Copyright © 2017 Elsevier Inc. Terms and Conditions