The Journal of Organic Chemistry
Note
2H), 7.68 (d, J = 3.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 52.3,
82.0, 95.7, 122.2, 128.5, 129.1, 130.1, 131.6, 132.2, 133.3, 133.8, 162.0.
Methyl 3-(Phenylethynyl)thiophene-2-carboxylate (3va).14 Col-
orless oil (94 mg, 97%); 1H NMR (400 MHz, CDCl3) δ 3.92 (s, 3H),
7.19 (d, J = 6.3 Hz, 1H), 7.32−7.37 (m, 3H), 7.44 (d, J = 5.1 Hz, 1H),
7.55−7.61 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 52.2, 84.0, 95.4,
123.0, 127.5, 128.4, 128.8, 130.5, 131.9, 132.1, 133.4, 161.9.
1-Methoxy-4-(4-tolylethynyl)benzene (3hb).10 Light-yellow solid
(88 mg, 99%), mp 119−122 °C; 1H NMR (400 MHz, CDCl3) δ 2.36
(s, 3H), 3.82 (s, 3H), 6.87 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 7.6 Hz,
2H), 7.40 (d, J = 8.0 Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ 20.5, 54.3, 87.2, 87.6, 113.0, 114.6, 119.5, 128.1,
130.3, 132.0, 137.0, 158.5.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to the National Natural Science Foundation of
China (21102134, 21172200) for financial support of this
research.
REFERENCES
■
(1) For selected reviews, see: (a) Sonogashira, K. J. Organomet. Chem.
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1-((4-Methoxyphenyl)ethynyl)-3-methylbenzene (3hc).5c Yellow
1
solid (85 mg, 96%), mp 43−45 °C; H NMR (400 MHz, CDCl3) δ
2.33 (s, 3H), 3.79 (s, 3H), 6.83−6.88 (m, 2H), 7.11 (d, J = 7.6 Hz,
1H), 7.21 (t, J = 7.6 Hz, 1H), 7.29−7.35 (m, 2H), 7.43−7.48 (m, 2H);
13C NMR (100 MHz, CDCl3) δ 21.0, 55.0, 88.0, 88.8, 113.8, 115.2,
123.2, 128.0, 128.3, 128.6, 131.8, 132.8, 137.7, 159.3.
́
2005, 44, 4442. (e) Chinchilla, R.; Najera, C. Chem. Rev. 2007, 107,
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(g) Plenio, H. Angew. Chem., Int. Ed. 2008, 47, 6954. (h) Chinchilla,
1-((4-Methoxyphenyl)ethynyl)-2-methylbenzene (3hd).6g Light-
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R.; Najera, C. Chem. Soc. Rev. 2011, 40, 5084.
(2) For representative papers on the palladium-catalyzed Sonogashira
reaction of aryl chlorides, see: (a) Eberhard, M. R.; Wang, Z.; Jensen,
C. M. Chem. Commun. 2002, 818. (b) Littke, A. F.; Fu, G. C. Angew.
Chem., Int. Ed. 2002, 41, 4176. (c) Choudary, B. M.; Madhi, S.;
Chowdari, N. S.; Kantam, M. L.; Sreedhar, B. J. Am. Chem. Soc. 2002,
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2003, 42, 5993. (e) Kollhofer, A.; Pullmann, T.; Plenio, H. Angew.
1
yellow solid (68 mg, 76%), mp 74−75 °C; H NMR (400 MHz,
CDCl3) δ 2.50 (s, 3H), 3.80 (s, 3H), 6.87 (d, J = 8.8 Hz, 2H), 7.12−
7.23 (m, 3H), 7.44−7.50 (m, 3H); 13C NMR (100 MHz, CDCl3) δ
20.5, 55.1, 86.8, 93.1, 113.8, 115.4, 123.1, 125.3, 127.8, 129.2, 131.4,
132.7, 139.7, 159.3.
2-((4-Methoxyphenyl)ethynyl)-1,3-dimethylbenzene (3he).15 Yel-
low solid (41 mg, 42%), mp 70−71 °C; 1H NMR (400 MHz, CDCl3)
δ 2.43 (s, 6H), 3.76 (s, 3H), 6.81 (d, J = 8.7 Hz, 2H), 6.94−7.08 (m,
3H), 7.40 (d, J = 8.7 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 21.2,
55.4, 85.8, 97.8, 114.0, 116.0, 123.3, 126.7, 127.4, 132.8, 140.0, 159.5.
1,2-Bis(4-methoxyphenyl)ethyne (3hf).7 Light-yellow solid (89
́ ́
Chem., Int. Ed. 2003, 42, 1056. (f) Komaromi, A.; Novak, Z. Chem.
Commun. 2008, 4968. (g) Anderson, K. W.; Buchwald, S. L. Angew.
Chem., Int. Ed. 2005, 44, 6173.
(3) (a) Park, J.; Park, E.; Kim, A.; Park, S.-A.; Lee, Y.; Chi, K. W.;
Jung, Y. H.; Kim, I. S. J. Org. Chem. 2011, 76, 2214. (b) Kim, Y.; Park,
A.; Park, K.; Lee, S. Tetrahedron Lett. 2011, 52, 1766.
(4) For representative papers on decarboxylative coupling, see:
(a) Moon, J.; Jeong, M.; Nam, H.; Ju, J.; Moon, J. H.; Jung, H. M.; Lee,
S. Org. Lett. 2008, 10, 945. (b) Moon, J.; Jang, M.; Lee, S. J. Org. Chem.
2009, 74, 1403. (c) Kim, H.; Lee, P. H. Adv. Synth. Catal. 2009, 351,
2827. (d) Zhao, D.-B.; Gao, C.; Su, X.-Y.; He, Y.-Q.; You, J.-S.; Xue, Y.
Chem. Commun. 2010, 46, 9049. (e) Li, T.-Y.; Qu, X.-M.; Zhu, Y.; Sun,
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J.-C. Adv. Synth. Catal. 2011, 353, 2731. (f) Reddy, P. V.; Srinivas, P.;
Annapurna, M.; Bhargava, S.; Wagler, J.; Mirzadeh, N.; Kantam, M. L.
Adv. Synth. Catal. 2013, 355, 705.
1
mg, 93%), mp 143−145 °C; H NMR (400 MHz, CDCl3) δ 3.82 (s,
6H), 6.84−6.89 (m, 4H), 7.42−7.47 (m, 4H); 13C NMR (100 MHz,
CDCl3) δ 54.3, 86.9, 112.9, 114.7, 131.9, 158.4.
5-((4-Methoxyphenyl)ethynyl)benzo[1,3]dioxole (3hg).9 Yellow
1
solid (94 mg, 93%), mp 123−125 °C; H NMR (400 MHz, CDCl3)
δ 3.81 (s, 3H), 5.97 (s, 2H), 6.77 (d, J = 8.0 Hz, 1H), 6.86 (d, J = 8.4
Hz, 2H), 6.96 (d, J = 0.9 Hz, 1H), 7.00−7.05 (m, 1H), 7.44 (d, J = 8.8
Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 55.0, 87.5, 87.7, 101.0,
108.2, 111.2, 113.7, 115.2, 116.6, 125.8, 132.7, 147.2, 147.4, 159.2.
1-(4-((4-Methoxyphenyl)ethynyl)phenyl)ethanone (3hh).16 White
solid (78 mg, 78%), mp 125−128 °C; 1H NMR (400 MHz, CDCl3) δ
2.61 (s, 3H), 3.84 (s, 3H), 6.90 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 8.8
Hz, 2H), 7.58 (d, J = 8.0 Hz, 2H), 7.93 (d, J = 8.0 Hz, 2H); 13C NMR
(100 MHz, CDCl3) δ 26.4, 55.1, 87.3, 92.7, 113.9, 114.4, 128.0, 128.4,
131.2, 133.0, 135.6, 159.8, 197.1.
(5) For deacetonative Sonogashira coupling, see: (a) Chow, H.-F.;
Wan, C.-W.; Low, K.-H.; Yeung, Y.-Y. J. Org. Chem. 2001, 66, 1910.
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́
(c) Shirakawa, E.; Kitabata, T.; Otsuka, H.; Tsuchimoto, T.
Methyl 2-((4-Methoxyphenyl)ethynyl)benzoate (3hi).17 Colorless
1
Tetrahedron 2005, 61, 9878. (d) Yi, C. Y.; Hua, R. M.; Zeng, H. X.;
oil (62 mg, 58%); H NMR (CDCl3, 400 MHz) δ 3.76 (s, 3H), 3.89
Huang, Q. F. Adv. Synth. Catal. 2007, 349, 1738. (e) Csek
Novak, Z.; Kotschy, A. Tetrahedron 2008, 64, 975. (f) Hung, T.-T.;
Huang, C.-M.; Tsai, F.-Y. ChemCatChem 2012, 4, 540.
́
ei, M.;
(s, 3H), 6.82 (d, J = 8.8 Hz, 2H), 7.24−7.32 (m, 1H), 7.35−7.49 (m,
3H), 7.55 (d, J = 7.5 Hz, 1H), 7.89 (d, J = 7.2 Hz, 1H); 13C NMR
(100 MHz, CDCl3) δ 52.2, 55.3, 87.1, 94.6, 114.0, 115.4, 124.1, 127.5,
130.5, 131.6, 131.7, 133.3, 133.8, 159.9, 166.8.
́
(6) (a) Huo, S.-Q.; Wu, Y.-J.; Du, C.-X.; Zhu, Y.; Yuan, H.-Z.; Mao,
X.-A. J. Organomet. Chem. 1994, 483, 139. (b) Yang, F.; Cui, X.-L.; Li,
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Cui, X.-L.; Yang, E.-B.; Yang, F.; Wu, Y.-J. Tetrahedron 2010, 66, 4022.
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Chem. 2010, 75, 6244.
1-Methoxy-4-((4-nitrophenyl)ethynyl)benzene (3hj).10 Yellow
1
solid (76 mg, 75%), mp 110−111 °C; H NMR (400 MHz, CDCl3)
δ 3.85 (s, 3H), 6.91 (d, J = 8.8 Hz, 2H), 7.50 (d, J = 8.8 Hz, 2H), 7.63
(d, J = 8.4 Hz, 2H), 8.20 (d, J = 8.8 Hz, 2H); 13C NMR (100 MHz,
CDCl3) δ 28.7, 54.3, 85.6, 94.1, 113.2, 122.6, 129.7, 131.0, 132.4,
145.7, 159.4.
ASSOCIATED CONTENT
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S
* Supporting Information
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Copies of NMR spectra for all of the compounds. This material
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AUTHOR INFORMATION
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Corresponding Authors
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dx.doi.org/10.1021/jo4014657 | J. Org. Chem. XXXX, XXX, XXX−XXX