A convenient transformation of phenols into the corresponding aryl fluorosulfates is presented: the first protocol to completely circumvent direct handling of gaseous sulfuryl fluoride (SO2F2). The proposed method employs 1,1′-sulfonyldiimidazole as a precursor to generate near-stoichiometric amounts of SO2F2 gas using a two-chamber reactor. With NMR studies, it was shown that this ex situ gas evolution is extremely rapid, and a variety of phenols and hydroxylated heteroarenes were fluorosulfated in good to excellent yields.
Ex Situ Generation of Sulfuryl Fluoride for the Synthesis of Aryl Fluorosulfates
Cedrick Veryser‡ 
, Joachim Demaerel‡, Vidmantas Bieliu̅nas, Philippe Gilles, and Wim M. De Borggraeve*
, Joachim Demaerel‡, Vidmantas Bieliu̅nas, Philippe Gilles, and Wim M. De Borggraeve*
Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Box 2404, 3001 Leuven, Belgium
Org. Lett., Article ASAP
DOI: 10.1021/acs.orglett.7b02522
*E-mail: wim.deborggraeve@kuleuven.be.
4-fluoro-[1,1'-biphenyl]-4-yl sulfurofluoridate (compound 1)
General procedure A was followed using 192 mg of 4-fluoro-4’-hydroxybiphenyl (98 wt%, 1.0 mmol,
1.0 eq.). The crude reaction mixture was purified by solid-phase flash column chromatography on
silicagel (heptane, 100%). The title compound was obtained as a white solid (258 mg, 96%).
Rf = 0.39 (heptane/ethyl acetate, 9/1). Melting point = 47 – 49 °C.
1
H NMR (400 MHz, CDCl3): 7.62 (d,
J = 8.5 Hz, 1H), 7.52 (dd, J = 8.1, 5.5 Hz, 1H), 7.41 (d, J = 8.5 Hz, 1H), 7.16 (t, J = 8.5 Hz, 1H).
13C NMR
(101 MHz, CDCl3): δ 163.05 (d, J = 247.9 Hz), 149.51, 141.17, 135.55 (d, J = 3.3 Hz), 129.06, 128.98,
121.42, 116.13 (d, J = 21.6 Hz).
19F NMR (376 MHz, CDCl3): δ 37.18, -114.68 (m).
IR (neat) cm-1
: 1437,
1232, 921, 815.
CHN: calculated for C12H8F2O3S: C 53.33%, H 2.98%, N 0.00%; found: C 53.43%, H 3.26%,
N 0.00%.
