Aromatic Halogenation Using N-Halosuccinimide and PhSSiMe₃ or PhSSPh

Abstract

We developed a mild aromatic halogenation reaction using a combination of N-halosuccinimide and PhSSiMe3 or PhSSPh. Less reactive aromatic compounds, such as methyl 4-methoxybenzoate, were brominated with PhSSiMe3 or PhSSPh and N-bromosuccinimide in high yields. No reaction was observed in the absence of PhSSiMe3 or PhSSPh. This method is also applicable to chlorination reactions using N-chlorosuccinimide and PhSSPh.

Recent Update on Transition Metal‐Free C(sp2)−H Bond Halogenation in (Hetero) Arenes

“…An interesting methodology [54] was depicted by Maegawa et al . for halogenation of arenes ( 65 ) under transition metal‐free condition.…”

Nickel(II)- and Silver(I)-Catalyzed C–H Bond Halogenation of Anilides and Carbamates

“…During the optimization study we found that when silver acetate was used instead of NiCl 2 •6H 2 O, as the catalyst in the presence of MSA in toluene at 50 °C, the desired product was obtained in 53% yield (entry 16). We then optimized the reaction conditions further by using silver-based catalysts, and competitive results were obtained with 10 mol% of Ag 2 CO 3 in the presence of 3.0 equivalent of MSA (entries [16][17][18][19][20][21][22][23][24][25][26][27]. Unfortunately, the reaction was not successful in water as the solvent (see the Supporting Information for details).…”

“…: m/z (%) = 251 (6), 249 (24), 247 (18) [M + ], 209 (33), 207 (100), 205 (90), 168 (30), 125 (15), 90 ( 14), 63 (28), 43 (65).…”

Added catalyst-free, versatile and environment beneficial bromination of (hetero)aromatics using NBS in WEPA

“…However, majority of these procedures require added catalysts, oxidants, nonconventional solvents, reagents or large reaction times were occasionally operated at harsh conditions. Most recently, NBS/PhSSPh (or PhSSiMe 3 ) [19], NBS/indoles [20], NBS/hexafluoroisopropanol [21], NBS/I 2 [22], NaBr/ H 2 O 2 /AcOH [23] and 1,2-ethanediylbis(triphenylphosph onium)-ditribromide [24] were found attractive. Nevertheless, these also suffer with the necessity of catalysts, expensive solvents, oxidants or large reaction times.…”