RSS-Feed abonnieren
DOI: 10.1055/s-0028-1088216
Synthesis of Tetrasubstituted Furans via Sequential Pd(OAc)2/Zn(OTf)2-Catalyzed Oxidation and Cyclization of Aromatic Alkynes with Molecular Oxygen
Publikationsverlauf
Publikationsdatum:
16. März 2009 (online)
![](https://www.thieme-connect.de/media/synlett/200906/lookinside/thumbnails/10.1055-s-0028-1088216-1.jpg)
Abstract
The development of a new method for the synthesis of tetrasubstituted furans using aromatic alkynes is reported. The strategy involves a tandem process of palladium-catalyzed oxidation and Zn(OTf)2-catalyzed cyclization in the presence of molecular oxygen.
Key words
synthesis - tetrasubstituted furans - aromatic alkynes - palladium-catalyzed - oxidation - cyclization
- Supporting Information for this article is available online:
- Supporting Information
-
1a
Hou XL.Yang Z.Wong HNC. In Progress in Heterocyclic Chemistry Vol. 15:Gribble GW.Gilchrist TL. Pergamon; Oxford: 2003. p.167-205 -
1b
Merritt AT.Ley SV. Nat. Prod. Rep. 1992, 9: 243 -
1c
Padwa A.Ishida M.Muller CL.Murphree SS. J. Org. Chem. 1992, 57: 1170 -
1d
Sargent MV.Dean FM. In Comprehensive Heterocyclic Chemistry Vol. 3:Bird CW.Cheeseman GWH. Pergamon Press; Oxford UK: 1984. p.599-656 -
1e
Dean FM. In Advances in Heterocyclic Chemistry Vol. 31:Katritzky AR. Academic Press; New York: 1983. p.237-344 -
1f
Natural Products
Chemistry
Vol. 1-3:
Nakanishi K.Goto T.Ito S.Natori S.Nozoe S. Kodansha, Ltd.; Tokyo: 1974. -
2a
Friedrichsen W. In Comprehensive Heterocyclic Chemistry II Vol. 2:Katritzky AR.Rees CW.Scriven EFV. Pergamon; Oxford: 1996. p.351-393 -
2b
Paquette LA.Astles PC. J. Org. Chem. 1993, 58: 165 -
2c
Lipshutz BH. Chem. Rev. 1986, 86: 795 -
3a
Nakano M.Tsurugi H.Satoh T.Miura M. Org. Lett. 2008, 10: 1851 -
3b
Kirsch SF. Org. Biomol. Chem. 2006, 4: 2076 -
3c
Kawai H.Oi S.Inoue Y. Heterocycles 2006, 67: 101 -
3d
Brown RCD. Angew. Chem. Int. Ed. 2005, 44: 850 -
3e
Jeevanandam A.Ghule A.Ling Y.-C. Curr. Org. Chem. 2002, 6: 841 -
3f
Friedrichsen W. Furans and Benzo Derivatives: Synthesis, In Comprehensive Heterocyclic Chemistry II Vol. 2:Katritzky AR.Rees CW.Scriven EFV. Pergamon Press; Oxford: 1996. p.351-394 - For selected examples, see:
-
4a
Arimitsu S.Jacobsen JM.Hammond GB. J. Org. Chem. 2008, 73: 2886 -
4b
Sniady A.Durham A.Morreale MS.Wheeler KA.Dembinski R. Org. Lett. 2007, 9: 1175 -
4c
Zhou C.-Y.Chan PWH.Che C.-M. Org. Lett. 2006, 8: 325 -
4d
Ma S.Gu Z.Yu Z. J. Org. Chem. 2005, 7: 6291 -
4e
Suhre MH.Reif M.Kirsch SF. Org. Lett. 2005, 7: 3925 -
4f
Sromek AW.Rubina M.Gevorgyan V. J. Am. Chem. Soc. 2005, 127: 10500 -
4g
Sniady A.Wheeler KA.Dembinski R. Org. Lett. 2005, 7: 1769 -
4h
Hashmi ASK.Sinha P. Adv. Synth. Catal. 2004, 346: 432 -
4i
Sromek AW.Kel’in AV.Gevorgyan V. Angew. Chem. Int. Ed. 2004, 43: 2280 -
4j
Trost BM.McIntosh MC. J. Am. Chem. Soc. 1995, 117: 7255 -
4k
Hashmi ASK. Angew. Chem., Int. Ed. Engl. 1995, 34: 1581 -
5a
Feng X.Tan Z.Chen D.Shen Y.Guo C.Xiang J.Zhu C. Tetrahedron Lett. 2008, 49: 4110 -
5b
Sanz R.Miguel D.Martinez A.Alvarez-Gutierrez JM.Rodriguez F. Org. Lett. 2007, 9: 727 -
5c
Duan X.-H.Liu X.-Y.Guo L.-N.Liao M.-C.Liu M.-W.Liang Y.-M. J. Org. Chem. 2005, 70: 6980 - 6
Wang A.Jiang H. J. Am. Chem. Soc. 2008, 130: 5030 - The formation of 1,4-dione from tetraphenylcyclobuta-dienenickel and palladium complex, see:
-
11a
Eisch JJ.Galle JE.Aradi AA.Boleslawski MP. J. Organomet. Chem. 1986, 312: 399 -
11b
Hoberg H.Fröhlich C. J. Organomet. Chem. 1980, 197: 105 - For selected examples on cyclocondensation of 1,4-dicarbonyl compounds to synthesize furans, see:
-
12a
Yin G.Wang Z.Chen A.Gao M.Wu A.Pan Y. J. Org. Chem. 2008, 73: 3377 -
12b
Banik BK.Samajdar S.Banik I. J. Org. Chem. 2004, 69: 213 -
12c
Kiryanov AA.Sampson P.Seed AJ. J. Org. Chem. 2001, 66: 7925 -
12d
Trost BM.Doherty GA. J. Am. Chem. Soc. 2000, 122: 3801 - 13
Nakano M.Tsurugi H.Satoh T.Miura M. Org. Lett. 2008, 10: 1851 - 14
Li ZF.Zhang YM.Liu YK. J. Indian Chem. Soc. 2002, 79: 188 - 15
Krepski LR.Heilmann SM.Rasmussen JK.Tumey ML.Smith HK. Synth. Commun. 1986, 16: 377 - 16
Wilson RM.Hengge AC.Ataei A.Ho DM. J. Am. Chem. Soc. 1991, 113: 7240
References and Notes
General Experimental
Procedure
The reaction was carried out in a HF-15
autoclave. Pd(OAc)2 (4.49 mg, 0.02 mmol), Zn(OTf)2 (98.3
mg, 0.3 mmol), MeOH (3 mL), and alkyne (1 mmol) were added into
a 15 mL autoclave in sequence. Oxygen was pumped into the autoclave
by a cooling pump to reach the desired pressure, then the autoclave
was heated by oil bath under magnetic stirring for the desired reaction
time. After the reaction finished, the autoclave was allowed to
cool to 0 ˚C. Residual O2 was vented,
and the surplus was filtrated and condensed under reduced pressure.
The product was purified by chromatography on a SiO2 column
using light PE-CH2Cl2
as
eluent.
Spectroscopic Data
for Tetrasubstituted Furans
2,3,4,5-Tetrakis(4-methoxyphenyl)furan
¹³
Mp 206-208 ˚C. ¹H
NMR (400 MHz, CDCl3): δ = 3.78 (s, 12
H), 6.77 (d, J = 6.4
Hz, 4 H), 6.79 (d, J = 7.2
Hz, 4 H), 7.04 (d, J = 8.8
Hz, 4 H), 7.42 (d, J = 9.2
Hz, 4 H) ppm.
¹³C NMR (100
MHz, CDCl3): δ = 125.1, 125.8, 127.1,
127.3, 128.3, 128.5, 130.4, 130.9, 133.1, 147.7 ppm. MS (EI, 70 eV): m/z (%) = 492
(28) [M+], 318 (100), 275
(31), 135 (47).
2,3,4,5-Tetrakis(4-fluorophenyl)furan
¹4
¹H NMR (400
MHz, CDCl3): δ = 6.93 (m, 8 H), 7.05-7.08 (m,
4 H), 7.41-7.44 (m, 4 H) ppm. ¹³C
NMR (100 MHz, CDCl3): δ = 115.6 (t, J = 80 Hz),
123.5, 126.7, 127.6, 127.7, 128.6, 131.9, 147.1, 160.9, 163.4 ppm.
MS (EI, 70 eV):
m/z (%) = 444
(100) [M+], 321 (73), 123
(69), 95 (55).
2,3,4,5-Tetrakis[4-(trifluoromethyl)phenyl]furan
¹³
Mp
195-197 ˚C. ¹H NMR (400 MHz,
CDCl3): δ = 7.24 6 (d, J = 8.0 Hz,
4 H), 7.55-7.57 (m, 12 H) ppm. ¹³C
NMR (100 MHz, CDCl3): δ = 119.9, 122.6,
125.1, 125.3, 125.7, 125.9, 126.2, 127.3, 128.0, 129.0, 129.8, 129.9,
130.1, 130.5, 130.8, 133.0, 135.6, 148.0 ppm. MS (EI, 70 eV): m/z (%) = 644
(46) [M+], 471 (13), 173 (100),
145 (33).
2,3,4,5-Tetra-
m
-tolylfuran
¹5
Mp 100-102 ˚C. ¹H
NMR (400 MHz, CDCl3): δ = 2.17 (s,
6 H), 2.27 (s, 6 H), 6.91-7.22 (m, 12 H), 7.62-7.66
(m, 4 H) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 21.3,
29.7, 123.0, 127.0, 127.6, 127.9, 128.1, 129.0, 129.2, 130.1, 130.2,
133.7, 135.3, 136.4, 137.9, 138.14, 144.2 ppm. MS (EI, 70 eV):
m/z (%) = 428
(100) [M+], 309 (21), 119
(65), 91 (18).
Procedure for Cyclization
of 1,4-Dione A
The reaction was carried out in a HF-15
autoclave. Pd(OAc)2 (4.49 mg, 0.02 mmol), Zn(OTf)2 (98.3
mg, 0.3 mmol), MeOH (3 mL), and 1,4-dione A (388
mg, 1 mmol) were added into a 15 mL autoclave in sequence. Oxygen
was pumped into the autoclave by a cooling pump to reach the desired
pressure, then the autoclave was heated by oil bath under magnetic
stirring for the desired reaction time. After the reaction finished,
the autoclave was allowed to cool to
0 ˚C. Oxygen
was vented, and the surplus was filtrated and condensed under reduced
pressure. The product was purified by chromatography on a SiO2 column
using light PE-CH2Cl2 as eluent to
give 2a in 72% yield.
Spectroscopic
Data for (
Z
)-1,2,3,4-Tetraphenylbut-2-ene-1,4-dione
¹6
Mp
216-217 ˚C. ¹H NMR (400 MHz,
CDCl3): δ = 7.14-7.40 (m,
16 H), 7.82-7.84 (m, 4 H) ppm. ¹³C
NMR (100 MHz, CDCl3): δ = 128.3, 128.4,
128.5, 128.6, 129.8, 130.0, 133.0, 135.2, 136.3, 144.6, 196.9 ppm.
MS (EI, 70 eV): m/z (%) = 388
(12) [M+], 178 (9), 105 (100),
77 (43).