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Synlett 2008(15): 2331-2333
DOI: 10.1055/s-2008-1077977
DOI: 10.1055/s-2008-1077977
LETTER
© Georg Thieme Verlag
Stuttgart ˙ New York
Regioselective Synthesis of Functionalized 3-(Methylthio)phenols by the First Formal [3+3] Cyclocondensations of 1,3-Bis(trimethylsilyloxy)-1,3-butadienes with 1,1-Bis(methylthio)-1-en-3-ones
Weitere Informationen
Received
21 April 2008
Publikationsdatum:
15. Juli 2008 (online)
Publikationsverlauf
Publikationsdatum:
15. Juli 2008 (online)
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Abstract
The [3+3] cyclocondensation of 1,3-bis(silyl enol ethers) with 1,1-bis(methylthio)-1-en-3-ones results in the regioselective formation of 3-(methylthio)phenols. The products represent useful synthetic building blocks, which are not readily available by other methods.
Key words
arenes - cyclizations - regioselectivity - silyl enol ethers
-
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Typical Procedure:
Synthesis of Ethyl 4-Ethyl-6-hydroxy-3-methyl-2-(methylthio)benzoate
(4b)
To a solution of 2b (0.190 g, 1.0 mmol) and 3b (0.549
g, 2.0 mmol) in CH2Cl2 (2 mL) was added TiCl4 (0.11
mL, 1.0 mmol) at -78 ˚C under argon.
The temperature of the reaction mixture was allowed to rise to 20 ˚C
during 14 h, and an aq HCl solution (10%, 10 mL) was added.
The organic layer was separated, and the aqueous layer was extracted
with CH2Cl2 (3 × 10
mL). The combined organic layers were dried (Na2SO4),
filtered, and concentrated in vacuo. After column chromatography
(SiO2, heptane-EtOAc = 10:1), 4b was obtained as a colorless solid (227 mg,
89%); mp 120-121 ˚C; Rf
= 0.39
(heptane-EtOAc = 3:1). ¹H
NMR (250 MHz, CDCl3): δ = 9.06
(s, 1 H, OH), 6.78 (s, 1 H, ArH), 4.43 (q, ³
J = 7.1 Hz,
2 H, OCH2), 2.60 (q, ³
J = 7.5 Hz,
2 H, ArCH2), 2.45 (s, 3 H, ArCH3), 2.28 (s,
3 H, SCH3), 1.41 (t, ³
J = 7.1 Hz,
3 H, OCH2CH
3),
1.18 (t, ³
J = 7.5
Hz, 3 H, ArCH2CH
3). ¹³C
NMR (300 MHz, CDCl3): δ = 170.2
(C=O), 156.9 (CO), 148.8, 136.2, 132.7, 117.3 (CAr),
116.9 (CHAr), 61.8 (OCH2), 27.6 (ArCH2),
20.0, 16.2, 14.0, 13.8 (CH3). IR (ATR): ν = 3298
(OH), 1699 (C=O) cm-¹.
MS (EI, 70 eV): m/z (%) = 254
(39) [M+], 209 (21), 208 (100),
193 (8), 180 (27), 165 (32). Anal. Calcd for C13H18O3S
(254.10): C, 61.39; H, 7.13. Found: C, 61.35; H, 7.27
- 24 CCDC-685823 contains all crystallographic
details of this publication and is available free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html
or can be ordered from the following address: Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033;
or deposit@ccdc.cam.ac.uk