Oxidative para-Triflation of Acetanilides

Abstract

Direct triflation of acetanilide derivatives with silver triflate has been accomplished under mild iodine(III)-mediated oxidative conditions. The reaction shows excellent regioselectivity for the para position and tolerates a range of ortho and meta substituents on the aromatic ring. This method is also compatible with the preparation of arylnonaflates in synthetically useful yields.

Site-Selective C–H Functionalization of (Hetero)Arenes via Transient, Non-symmetric Iodanes

“…Notably, TfOH alone facilitates iodane-mediated C-H oxytriflation to afford aryl triflate 1, without the need for stoichiometric AgOTf. 52 Similarly, C-H oxy-sulfonylations are observed with TsOH and MsOH, which afford tosylate 2 and mesylate 3, also without additional promoters (e.g., BF 3 ). 53 Importantly, aqueous mineral acids, HBr and HCl, afford halogenated arenes, 4 and 5, with high efficiency (up to 88% yield) and para-selectivity (>20:1).…”

Palladium Catalyzed Direct Acylation of Iodo‐Acetanilides/Iodo‐Phenyl Acetates: Domino One‐Pot Synthesis of 2‐Quinolinones

“…Iodo acetanilides and iodophenyl acetates 1a – 1j was synthesized in accordance to reports in the literature from the corresponding iodo anilines and iodo phenols, which are commercially available.…”

Palladium-Catalyzed C–P Bond-Forming Reactions of Aryl Nonaflates Accelerated by Iodide

“…Spectroscopic data were consistent with the literature. 29 1 H NMR (400 MHz, CDCl 3 ) δ 2.19 (s, 3H), 7.23 (d, J = 9.0 Hz, 2H), 7.41 (br s, 1H), 7.60 (d, J = 9.0 Hz, 2H); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 24.7 (CH 3 ), 121.1 (2 × CH), 122.1 (2 × CH), 138.0 (C), 145.7 (C), 168.6 (C); MS (ESI) m / z 456 (M + Na + , 100).…”