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DOI: 10.1055/s-0031-1289874
An Efficient Copper-Catalyzed One-Pot Synthesis of Diaryl Thioethers by Coupling of Arylboronic Acids with Potassium Ethyl Xanthogenate under Mild Conditions
Publication History
Publication Date:
11 November 2011 (online)
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Abstract
A simple and environmentally benign one-pot synthesis of diaryl thioethers by coupling of arylboronic acids with potassium ethyl xanthogenate through a double arylation process has been developed. The aryl thiols were generated in situ, and the reactions proceeded smoothly to give the corresponding products in good to excellent yields under very mild conditions.
Key words
diaryl thioethers - arylboronic acids - potassium ethyl xanthogenate - one-pot synthesis - copper-catalyzed
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References and Notes
Typical Procedure
for the Synthesis of Diaryl and Aryl Alkyl Thioethers
A
mixture of arylboronic acid (0.75 mmol), CuCl (3.7 mg, 0.0375 mmol),
potassium ethyl xanthogenate (120.2 mg, 0.75 mmol), and MeOH (3.0
mL) were taken in a flask at r.t. under N2. The reaction
mixture was stirred for a certain time under reflux conditions.
After disappearance of arylboronic acid (monitored by TLC), the
reaction mixture was allowed to cool down to r.t., KOH (168.3 mg,
3 mmol) and another arylboronic acid or alkyl halide (0.50 mmol
for unsym-metrical thioethers, 0.75 mmol for symmetrical diaryl thioethers)
were added, and the resulting mixture was further heated for a certain
time (monitored by TLC). After reaction, the mixture was extracted
with EtOAc and H2O. The organic layer was dried over
anhyd Na2SO4, and the solvent was removed
under reduced pressure. The crude residue was purified by column
chromatography on silica gel using EtOAc-hexanes as eluents
to give the corresponding thioethers. All the thioethers are known
compounds and identified by comparison of their physical and spectral
data with those of authentic samples.
Bis(4-Methoxyphenyl)sulfane
(3c)
Colorless oil. ¹H NMR (400
MHz, CDCl3): δ = 3.79 (s, 6 H), 6.81-6.86
(m, 4 H), 7.25-7.30 (m, 4 H). ¹³C
NMR (100 MHz, CDCl3): δ = 55.5, 114.9,
127.6, 132.9, 159.1. HRMS: m/z [M + H]+ calcd
for C14H15O2S: 247.0793; found: 247.0783.
(3-Methoxyphenyl)(phenyl)sulfane (5g)
Colorless
oil. ¹H NMR (400 MHz, CDCl3): δ = 3.73
(s, 3 H), 6.73-6.78 (m, 1 H), 6.83-6.85 (m, 1
H), 6.86-6.90 (m, 1 H), 7.17 (d, J = 8.4
Hz, 1 H), 7.20-7.31 (m, 3 H), 7.33-7.37 (m, 2
H). ¹³C NMR (100 MHz, CDCl3): δ = 55.4,
112.9, 116.0, 123.1, 127.4, 129.4, 130.1, 131.6, 135.4, 137.4, 160.2. HRMS: m/z [M + H]+ calcd
for C13H13OS: 217.0687; found: 217.0688.
Benzyl Phenyl Sulfide (Table 4, Entry 1)
White
solid; mp 40-42 ˚C. ¹H NMR
(400 MHz, CDCl3): δ = 4.11 (s, 2 H),
7.14-7.34 (m, 10 H). ¹³C NMR
(100 MHz, CDCl3): δ = 39.2, 126.5,
127.3, 128.6, 128.9, 129.0, 130.0, 136.5, 137.6. HRMS: m/z [M + K]+ calcd
for C13H12SK: 239.0297; found: 239.0289.