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DOI: 10.1055/s-0028-1083516
Regioselective Synthesis of 2-(Arylthio)benzoates by the First Catalytic [3+3] Cyclocondensations of 3-(Arylthio)-1-(trimethylsilyloxy)-1,3-butadienes with 1,1,3,3-Tetramethoxypropane
Publication History
Publication Date:
01 October 2008 (online)
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Abstract
2-(Arylthio)benzoates were regioselectively prepared by the first catalytic [3+3] cyclizations of 3-(arylthio)-1-(trimethylsilyloxy)-1,3-butadienes with 1,1,3,3-tetramethoxypropane.
Key Words
arenes - cyclizations - diaryl sulfides - regioselectivity - silyl enol ethers
-
1a
Behar V.Danishefsky SJ. J. Am. Chem. Soc. 1993, 115: 7017 -
1b
Toste FD.Still IWJ. J. Am. Chem. Soc. 1995, 117: 7261 -
1c
Davidson BS.Molinski TF.Barrows LR.Ireland CM. J. Am. Chem. Soc. 1991, 113: 4709 -
1d
Mori Y.Taneda S.Hayashi H.Sakushima A.Kamata K.Suzuki AK.Yoshino S.Sakata M.Sagai M.Seki K.-i. Biol. Pharm. Bull. 2002, 25: 145 -
1e
Davis RA.Sandoval IT.Concepcion GP.Moreira da Rocha R.Ireland CM. Tetrahedron 2003, 59: 2855 -
1f
Liu H.Fujiwara T.Nishikawa T.Mishima Y.Nagai H.Shida T.Tachibana K.Kobayashi H.Mangindaan REP.Namikoshi M. Tetrahedron 2005, 61: 8611 -
1g
Kaplan ML.Reents WD. Tetrahedron Lett. 1982, 23: 373 -
1h
Hosoya Y.Adachi H.Nakamura H.Nishimura Y.Naganawa H. Tetrahedron Lett. 1996, 37: 9227 - See, for example:
-
2a
Glass HB.Reid EE. J. Am. Chem. Soc. 1929, 51: 3428 -
2b
Dougherty G.Hammond PD.
J. Am. Chem. Soc. 1935, 57: 117 -
2c For the trifluoromethanesulfonic
acid catalyzed sulfurization of cycloalkanes, see:
Olah GA.Wang Q.Prakash GKS. J. Am. Chem. Soc. 1990, 112: 3697 - 3
Kemp DS.Carey RI.Dewan JC.Galakatos NG.Kerkman D.Leung S.-L. J. Org. Chem. 1989, 54: 1589 ; and references cited therein - 4
Chua M.Hoyer H. Z. Naturforsch., B 1965, 20: 416 -
5a
Baxter I.Ben-Haida A.Colquhoun HM.Hodge P.Kohnke FH.Williams DJ. Chem. Eur. J. 2000, 6: 4285 ; and references cited therein -
5b
Campbell JR. J. Org. Chem. 1964, 29: 1830 -
6a
Taniguchi N. J. Org. Chem. 2007, 72: 1241 -
6b
Fernández-Rodríguez MA.Shen Q.Hartwig JF. J. Am. Chem. Soc. 2006, 128: 2180 -
6c
Murata M.Buchwald SL. Tetrahedron 2004, 60: 7397 -
7a
Gendre F.Yang M.Diaz P. Org. Lett. 2005, 7: 2719 -
7b
Bates CG.Gujadhur RK.Venkataraman D. Org. Lett. 2002, 4: 2803 -
7c
Rábai J. Synthesis 1989, 523 -
8a
Hilt G.Lüers S. Synthesis 2003, 1784 -
8b
Hilt G.Lüers S.Harms K. J. Org. Chem. 2004, 69: 624 -
9a
Rashid MA.Reinke H.Langer P. Tetrahedron Lett. 2007, 48: 2321 -
9b
Rashid MA.Rasool N.Adeel M.Reinke H.Fischer C.Langer P. Tetrahedron 2008, 64: 3782 - 10 For a review on [3+3] cyclizations,
see:
Feist H.Langer P. Synthesis 2007, 327 - 11 For a review on 1,3-bis(silyloxy)-1,3-butadienes,
see:
Langer P. Synthesis 2002, 441 -
12a
Chan T.-H.Brownbridge P. J. Am. Chem. Soc. 1980, 102: 3534 -
12b
Brownbridge P.Chan T.-H.Brook MA.Kang GJ. Can. J. Chem. 1983, 61: 688 - 13
Mamat C.Büttner S.Trabhardt T.Fischer C.Langer P. J. Org. Chem. 2007, 72: 6273 - 14
Sher M.Ahmed Z.Rashid MA.Fischer C.Langer P. J. Org. Chem. 2007, 72: 6284 -
15a
Chan TH.Prasad CVC. J. Org. Chem. 1986, 51: 3012 -
15b
Chan TH.Prasad CVC. J. Org. Chem. 1987, 52: 110 - 16
Rashid MA.Rasool N.Iqbal I.Imran M.Langer P. Tetrahedron Lett. 2008, 49: 2466
References and Notes
Typical Experimental
Procedure
To a CH2Cl2 solution
(2 mL/mmol of 3) of 3 (1.5 mmol) and of 1,1,3,3-tetramethoxypropane
(1.0 mmol) was added TMSOTf (0.1 mmol) at -78 ˚C.
The solution was allowed to warm to 20 ˚C within
20 h. To the solution was added a diluted aq solution of HCl (15
mL). The organic and the aqueous layer were separated, and the latter
was extracted with CH2Cl2 (3 × 15
mL). The combined organic layers were dried (Na2SO4),
filtered, and the filtrate was concentrated in vacuo. The residue
was purified by chromatography.
Methyl
2-(Phenylthio)benzoate (5a)
Starting
with 1,1,3,3-tetramethoxypropane (0.33 mL,
2.0 mmol), 3a (843 mg, 3.0 mmol), TMSOTf (0.036 mL,
0.2
mmol), and CH2Cl2 (4 mL), 5a was
isolated as a highly viscous colourless oil (275 mg, 53%). ¹H
NMR (250 MHz, CDCl3): δ = 3.66
(s, 3 H, OCH3), 6.75 (dd, 1 H, ³
J = 7.20, 4
J = 1.87 Hz,
ArH), 7.06 (ddd, 1 H, ³
J = 7.20, 4
J = 1.87, 5
J = 0.92 Hz,
ArH), 7.16 (m, 2 H, ArH), 7.36 (m, 3 H, ArH), 7.48 (m, 2 H, ArH). ¹³C
NMR (62 MHz, CDCl3): δ = 52.1 (OCH3),
124.2 (ArCH), 126.7 (C), 127.4, 129.0 (ArCH), 129.7 (2C, ArCH),
131.1, 132.2 (ArCH), 124.6 (C), 135.5 (2C, ArCH), 143.1, 166.8 (C).
IR (neat): ν = 3056 (w), 2948 (w), 1711 (s), 1585
(m), 1562 (m), 1433 (s), 1246 (s), 1189 (m), 1056 (s), 738 (s),
688 (s)530 (m) cm-¹. GC-MS (EI,
70
eV): m/z (%) = 244
(100), 213 (76), 184 (55), 152 (16), 139 (10), 108 (8). HRMS (EI): m/z calcd for C14H12O2S [M+]:
244.05525; found: 244.05570.