Disulfide-based metal-free α-sulfanylation of ketones

Abstract

An eco-friendly methodology for the direct alpha-sulfanylation of ketones, has been developed. The procedure, based on the use of functionalized diaryldisulfides and catalyzed by D,L-proline, represents a mild and efficient approach for the preparation of alpha-arylthio-ketones

Pyrimidine Nucleosides with a Reactive (β-Chlorovinyl)sulfone or (β-Keto)sulfone Group at the C5 Position, Their Reactions with Nucleophiles and Electrophiles, and Their Polymerase-Catalyzed Incorporation into DNA

“…The 5-(β-keto)sulfones also react with disulfides in the presence of a TEA-trapping electrophilic phenylsulfenyl 48 ion. Thus, the treatment of 2′-deoxyuridine-derived sulfone 12 with phenyl disulfide (2 equiv) in the presence of TEA in MeCN led to the α-sulfanylation, affording 23 (36%) as a 1:1 mixture of diastereomers ( Scheme 3 , method A).…”

Insights into the Reactivity of 2-Hydroxycyclobutanones with Thiols Corroborated by Quantum Chemical DFT Investigations and NMR and Raman Analysis

“…Infrared spectra were recorded on FT-IR Bruker Equinox-55 or Thermo Fisher Scientific Nicolet IS50 FTIR spectrophotometers and are reported in wavenumbers (cm -1 ). 1 H and 13 C NMR spectra were obtained on Bruker DRX 600 ( 1 H, 600 MHz; 13 C, 150 MHz) or Varian 500 ( 1 H, 500 MHz; 13 C, 126 MHz) spectrometers at 27 °C using CDCl3 (internal reference = 7.26 ppm) as the solvent. 13 C NMR were recorded at 126 MHz (internal reference = 77.00 ppm) using CDCl3 as the solvent.…”

Sulfenylation of C–H Bonds for C–S Bond Formation under Metal‐Free Conditions

“…As is widely known, dl ‐proline has been extensively used as an asymmetric catalyst in organic chemistry. In 2015, Secci and co‐workers reported a new methodology for the direct α‐sulfenylation of ketones, catalyzed by dl ‐proline, in good to excellent yields and with high diastereo‐, regio‐, and chemoselectivity . Both cyclic and acyclic ketones reacted well (Scheme ).…”

“…In 2015, Secci and co-workers reported a new methodology for the direct α-sulfenylation of ketones, catalyzed by DL-proline, in good to excellent yields and with high diastereo-, regio-, and chemoselectivity. [24] Both cyclic and acyclic ketones reacted well (Scheme 17). DFT calculations revealed a direct correlation between the natural charge on the sulfur atom and the formation of keto sulfides through direct proline-based sulfenylation.…”