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DOI: 10.1055/s-2008-1078549
One-Pot Oxidative Conjugate Hydrothiocyanation-Hydrosulfenylation of Baylis-Hillman Alcohols Promoted by a Protic Ionic Liquid
Publication History
Publication Date:
02 July 2008 (online)
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Abstract
The first example of one-pot oxidative conjugate hydrothiocyanation-hydrosulfenylation of acrylic ester derived Baylis-Hillman alcohols, that is, methyl 3-aryl-3-hydroxy-2-methylenepropanoate, is reported. The reaction involves protic ionic liquid [Hmim]HSO4-mediated oxidation of Baylis-Hillman alcohols with NaNO3 to give methyl (E)-α-formylcinnamates followed by conjugate addition of sulfur-centered nucleophiles (NH4SCN/PhSH) to afford the corresponding methyl β-thiocyanato (or β-phenylsulfenyl)-α-formylhydrocinnamates diastereoselectively in 74-87% yields in a one-pot procedure. After isolation of the product, the ionic liquid [Hmim]HSO4 could be easily recycled for further use without any loss of efficiency.
Key words
Baylis-Hillman alcohols - conjugate addition - oxidation - protic ionic liquids - methyl cinnamates - stereoselective synthesis
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References and Notes
General Procedure
for the Synthesis of Methyl β-Thiocyanato-α-formylhydrocinnamates
3 and Methyl β-Phenylsulfenyl-α-formylhydrocinnamates
4
A mixture of BH alcohol 1 (1
mmol) and NaNO3 (1 mmol) was stirred in 1 mL of [Hmim]HSO4 at
80 ˚C for 1-3 h (Table
[²]
). The reaction mixture
was cooled to r.t. and NH4SCN or PhSH (1.1 mmol) was
added. The mixture was further stirred at r.t. for 2-3
h. After completion of the reaction (monitored by TLC), the product
was extracted with EtOAc (3 10 mL). The combined
extract was dried over MgSO4, filtered, concentrated
under reduced pressure, and purified by silica gel column chromatography
(hexane-EtOAc, 8.5:1.5) to afford the desired product 3 or 4. After isolation
of the product, the remaining ionic liquid was washed with Et2O
(2 10 mL) to remove any organic impurity, then
H2SO4 (2.1 mmol in the case of compound 3 and 1 mmol in the case of 4)
was added, the mixture was stirred at 80 ˚C for
1 h, and cooled to about -5 ˚C in an
ice-salt bath. The precipitated solid [Na2SO4,
(NH4)2SO4] was filtered
out, and the filtrate was dried under vacuum to afford the IL [Hmim]HSO4,
which was used in subsequent runs.
Data
of Representative Compounds
Compound 3a:
white solid, yield 78%, mp 104-105 ˚C.
IR (KBr): 3026, 2115, 1745, 1718, 1603, 1578, 1460, 1284, 1194,
764, 714 cm-¹. ¹H
NMR (400 MHz, CDCl3, TMS): d = 3.68
(dd, 1 H, J = 3.9,
2.1 Hz, 2-H), 3.82 (s, 3 H, MeOCO), 4.86 (d, 1 H, J = 3.9
Hz, 3-H), 7.14-7.32 (m, 5 Harom), 9.56 (d, 1
H, J = 2.1
Hz, CHO). ¹³C NMR (100 MHz, CDCl3,
TMS): d = 36.6, 63.9, 52.8, 112.4, 126.9,
128.6, 129.2, 140.9, 169.1, 198.3. MS (EI): m/z = 249 [M+].
Anal. Calcd (%) for C12H11NO3S:
C, 57.82; H, 4.45; N, 5.62. Found: C, 57.56; H, 4.57; N, 5.43.
Compound 4f: yellowish solid, yield 76%,
mp 132-133 ˚C. IR (KBr): 3055, 2932,
1746, 1721, 1586, 1520, 1345, 1280, 1186, 760, 710 cm-¹. ¹H
NMR (400 MHz, CDCl3, TMS): d = 3.72
(dd, 1 H, J = 3.9,
2.1 Hz, 2-H), 3.81 (s, 3 H, MeOCO), 4.68 (d, 1 H, J = 3.9
Hz, 3-H), 7.24-8.27 (m, 9Harom), 9.54 (d, 1
H, J = 2.1
Hz, CHO). ¹³C NMR (100 MHz, CDCl3,
TMS): d = 30.6, 52.7, 64.2, 121.6, 124.9, 127.4,
129.2, 129.8, 135.8, 148.2, 149.4, 169.0, 198.3. MS (EI): m/z = 345 [M+].
Anal. Calcd (%) for C17H15NO5S:
C, 59.12; H, 4.38; N, 4.06. Found: C, 59.33; H, 4.74; N, 3.89.
General Procedure
for the Synthesis of Methyl (
E
)-α-Formylcinnamates 2
A
stirred solution of BH alcohols 1 (1 mmol)
and NaNO3 (1 mmol) in 1 mL of [Hmim]HSO4 was
heated at 80 ˚C for 1-3 h (Table
[²]
). The reaction progress
was monitored by TLC. Upon completion, the reaction mixture was
cooled to r.t. and extracted with EtOAc (3 × 10
mL).The combined organic phase was dried over MgSO4,
filtered, and evaporated under reduced pressure. The resulting crude
product was purified by silica gel column chromatography using a
gradient mixture of hexane-EtOAc (8:2) as eluent to give
the pure cinnamates 2. The remaining ionic
liquid was recycled for subsequent runs as described above using
H2SO4 (1 mmol).¹6
Data of Representative Compound
Compound 2a: white solid, yield 80%, mp
91-92 ˚C. IR (KBr): 3076, 2809, 2740,
1724, 1684, 1578, 1462, 1286, 1190, 760, 712 cm-¹. ¹H
NMR (400 MHz, CDCl3, TMS): δ = 3.87
(s, 3 H, MeOCO), 7.48-7.70 (m, 3 Harom), 7.86
(s, 1 H, CHPh), 8.04-8.12 (m, 2 Harom), 9.66
(s, 1 H, CHO). ¹³C NMR (100 MHz, CDCl3,
TMS): δ = 52.6, 127.7, 129.4, 130.2,
131.3, 134.7, 154.6, 167.9, 187.6. MS (EI):
m/z = 190 [M+].
Anal. Calcd (%) for C11H10O3:
C, 69.46; H, 5.30. Found: C, 69.81; H, 5.14.