Iodine(III)-Mediated, Controlled Di- or Monoiodination of Phenols

Abstract

An oxidative procedure for the electrophilic iodination of phenols was developed by using iodosylbenzene as a nontoxic iodine­(III)-based oxidant and ammonium iodide as a cheap iodine atom source. A totally controlled monoiodination was achieved by buffering the reaction medium with K3PO4. This protocol proceeds with short reaction times, at mild temperatures, in an open flask, and generally with high yields. Gram-scale reactions, as well as the scope of this protocol, were explored with electron-rich and electron-poor phenols as well as heterocycles. Quantum chemistry calculations revealed PhII­(OH)·NH3 to be the most plausible iodinating active species as a reactive “I+” synthon. In light of the relevance of the iodoarene moiety, we present herein a practical, efficient, and simple procedure with a broad functional group scope that allows access to the iodoarene core unit.

NCBSI/KI: A Reagent System for Iodination of Aromatics through In Situ Generation of I-Cl

“…The experimental procedure followed for the synthesis of 2a using 2-methoxynaphthalene (1.15 g, 7.24 mmol) substrate produced 1.89 g (92% yield, 99% purity) as a light pink crystalline solid: mp 84−86 °C (lit. 50…”

“…The experimental procedure followed for the synthesis of 2a using 2-methoxynaphthalene (1.15 g, 7.24 mmol) substrate produced 1.89 g (92% yield, 99% purity) as a light pink crystalline solid: mp 84–86 °C (lit . mp 86–88 °C); 1 H NMR (400 MHz, CDCl 3 ) δ 8.14 (d, J = 8.6 Hz, 1H), 7.83 (d, J = 8.9 Hz, 1H), 7.74 (d, J = 8.1 Hz, 1H), 7.54 (t, J = 7.1 Hz, 1H), 7.38 (t, J = 7.5 Hz, 1H), 7.21 (d, J = 8.9 Hz, 1H), 4.02 (s, 3H).…”

Interplay of Hydrogen and Halogen Bonding in the Crystal Structures of 2,6‐Dihalogenated Phenols

“…[6][7][8][9] Aryl halides are of particular importance as electrophiles in CÀ C coupling reactions, [10][11][12][13] which makes the development of new, efficient synthetic strategies a worthwhile task. [14][15][16][17][18][19] In recent years, efforts have been made to develop new synthetic routes particularly to halogenated phenols, [20][21][22][23][24] which have also been used as antibacterial agents. [25] Halogen bonds have been studied for a long time and are still a research topic of highest interest.…”

The Diaryliodonium(III) Salts Reaction With Free-Radicals Enables One-Pot Double Arylation of Naphthols

“…Considering the synthetic importance of aryl phenols, we focused on this target as a part of our research in the development of new iodine(III)-based reactions (Nahide et al, 2018;Satkar et al, 2018Satkar et al, , 2019Juárez-Ornelas et al, 2019;Segura-Quezada et al, 2019). Herein, we report the recent advances of our approach using Ar 2 IX.…”