Practical, mild and efficient electrophilic bromination of phenols by a new I(iii)-based reagent: the PIDA–AlBr₃system

Abstract

A practical electrophilic bromination procedure for the phenolic core was developed under efficient and very mild reaction conditions. The new I(iii)-based brominating reagent PhIOAcBr operationally easy to prepare by mixing PIDA and AlBr3 was used.

Electrophilic Bromination in Flow: A Safe and Sustainable Alternative to the Use of Molecular Bromine in Batch

“…To circumvent these problems, brominations are often performed with alternative bromination reagents, most commonly organic molecules containing a Br(I)-species. This bromine(I) can be bonded to nitrogen (e.g., N-bromosuccinimide or tribromoisocyanuric acid [7,8,9]); iodine(III) [10]; carbon (e.g., CBr 4 [11]), or even three bromine atoms bonded together in Br 3 − , countered by an organic cation, possibly forming an ionic liquid [12,13]. Although these alternatives provide a number of benefits, especially for academic laboratories, they still are far from perfect—they are expensive, are often still toxic and unsustainable, produce organic by-products, and most of them use molecular bromine in their synthesis, thus not solving but only shifting the problem [9,14,15].…”

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.…”

Preparation and Synthetic Application of Naproxen-Containing Diaryliodonium Salts

“…Significant efforts have been made in the structural modification of naproxen [ 4 , 5 ], including the introduction of fluorine atom into the side chain of this molecule or an esterification process of the carboxylic acid with alcohols ( Figure 1 A, Ia ) [ 6 , 7 ]. There have also been a few scattered methods for the functionalization of the aromatic ring of naproxen, including the introduction of the halogen atom into the aromatic ring ( Figure 1 B, Ib – Id ) [ 8 , 9 , 10 ]. Some special functionalization has also been applied to the aromatic ring, including hydroxylation and the incorporation of the SCF 3 group ( Figure 1 B, Ie , If ) [ 11 , 12 ].…”