Imination of Sulfides and Sulfoxides with Sulfonylimino‐λ³‐Bromane under Mild, Metal‐Free Conditions

Abstract

Exposure of sulfides and sulfoxides to trifluoromethanesulfonylimino(aryl)-lambda(3)-bromane in dichloromethane at 0 degrees C results in a facile transfer of the sulfonylimino group to sulfur atoms and affords N-triflylsulfilimines and -sulfoximines in high yields under transition-metal-free conditions. Imination of (R)-methyl p-tolyl sulfoxide proceeded with predominant retention of configuration at the stereogenic sulfur center. The Hammett plot afforded rho values of -0.58 for para-substituted thioanisoles and -0.49 for their equivalent sulfoxides, which suggests a buildup of positive charge on the sulfur atoms of sulfides and sulfoxides in the transition state. Calculations suggest a bimolecular nucleophilic-substitution mechanism on the negatively charged nitrogen atom of the sulfonylimino-lambda(3)-bromane, which involves the attack of a sulfide from the opposite side to bromine(III).

Halogens

“…[56][57][58][59][60] Elemental halogens Fully 30% of the top pharmaceuticals in sale contain a fluorine atom as highlighted by a recent review. 1 Furthermore, the innate nuclear properties of 18 F as a radiotracer for positron emission tomography (PET) and 19 F as an active nucleus for magnetic resonance imaging (MRI) fosters development of methodology for the selective fluorination of biomolecules.…”

CO2-activated NaClO-5H2O enabled smooth oxygen transfer to iodoarene: a highly practical synthesis of iodosylarene

“…. 43 Mp 117-118 °C; 1 H NMR (500 MHz, CDCl3): δ 7.84 (d, J = 8.4 Hz, 2H), 7.72-7.60 (m, 3H), 3.02 (s, 3H); 19 F NMR (470 MHz, CDCl3): δ -78.9 ppm (s, 3F).…”

Trifluoromethanesulfonamide vs. Non-Fluorinated Sulfonamides in Oxidative Sulfamidation of the C=C Bond: An In Silico Study

“…Iodinanes ArI=NSO 2 Ar' are used mainly for aziridination of alkenes [9,[49][50][51]. Note that aziridination with imino-λ 3 -bromane CF 3 SO 2 N=BrC 6 H 4 CF 3 is one of a few methods of synthesis of N-triflylaziridines [15,52,53]. Aziridines can be intermediate products, leading finally to various heterocycles.…”