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F. Shahsavari et al.
Letter
Synlett
References and Notes
2 H), 3.78 (s, 3 H), 3.89 (s, 3 H), 6.38 (s, 1 H), 7.23 (d, 3J = 7.0 Hz,
2 H), 7.28–7.332 (m, 3 H). 13C NMR (125.7 MHz, CDCl3): δ = 45.6
(CH2), 53.3 (OCH3), 54.7 (OCH3), 127.7 (CH), 128.7 (2 CH), 129.3
(2 CH), 131.9 (CH), 136.1 (C), 147.7 (C), 165.5 (C=O), 167.0
(C=O). MS: m/z (%) = 234 (M+, 3), 219 (21), 188 (47), 116 (71), 91
(100). Anal. Calcd for C13H14O4 (234.25): C, 66.66; H, 6.02.
Found: C, 66.95; H, 6.41.
(1) Godula, K.; Sames, D. Science 2006, 312, 67.
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1937.
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4123.
Dimethyl 2-(4-Chlorobenzyl)fumarate (3b)
Colorless oil; yield: 0.23 g (86%). IR (KBr): 3014, 2971, 1735,
1721, 1316, 1135 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.46 (s,
2 H), 3.75 (s, 3 H), 3.85 (s, 3 H), 6.42 (s, 1 H), 7.32 (app d, 3J = 7.1
Hz, 2 H), 7.45 (app d, 3J = 7.1 Hz, 2 H). 13C NMR (125.7 MHz,
CDCl3): δ = 48.6 (CH2), 53.3 (OCH3), 54.3 (OCH3), 128.6 (2 CH),
129.0 (2 CH), 133.8 (CH), 134.0 (C), 135.6 (C), 147.3 (C), 165.4
(C=O), 167.1 (C=O). MS: m/z (%) = 268 (M+, 1), 253 (10), 209 (29),
143 (57), 125 (100), 88 (38). Anal. Calcd for C13H13ClO4 (268.69):
C, 58.11; H, 4.88; Cl, 13.19. Found: C, 58.49; H, 5.19; Cl, 13.54.
Dimethyl 2-[(1-Naphthyl)methyl]fumarate (3h)
(11) Varma, R. S.; Naicker, K. P. Green Chem. 1999, 1, 247.
(12) Wang, S.; Qian, Q.; Gong, H. Org. Lett. 2012, 14, 3352.
(13) Ueda, M.; Nishimura, K.; Kashima, R.; Ryu, I. Synlett 2012, 23,
1085.
(14) Dunet, G.; Knochel, P. Synlett 2007, 1383.
(15) Jia, C.; Piao, D.; Oyamada, J.; Lu, W.; Kitamura, T.; Fujiwara, Y.
Science 2000, 287, 1992.
(16) Liu, H.; Shi, G.; Pan, S.; Jiang, Y.; Zhang, Y. Org. Lett. 2013, 15,
4098.
(17) Feng, J.; Liang, S.; Chen, S.-Y.; Zhang, J.; Fu, S.-S.; Yua, X. Q. Adv.
Synth. Catal. 2012, 354, 1287.
Pale-yellow oil; yield: 0.24 g (86%). IR (KBr): 3043, 2978, 1728,
1716, 1361, 1182 cm–1. 1H NMR (500.1 MHz, CDCl3): δ = 3.76 (s,
3 H), 3.89 (s, 3 H), 4.11 (s, 2 H), 6.43 (s, 1 H), 7.06 (d, 3J = 6.6 Hz,
3
1 H), 7.25–7.34 (m, 3 H), 7.78 (d, 3J = 7.0 Hz, 1 H), 7.86 (d, J =
7.1 Hz, 1 H) 7.95 (t, 3J = 6.7 Hz, 1 H). 13C NMR (125.7 MHz,
CDCl3): δ = 39.2 (CH2), 51.4 (OCH3), 57.4 (OCH3), 127.7 (CH),
127.8 (CH), 128.3 (CH), 128.7 (CH), 128.9 (C), 129.1 (C), 129.2
(CH), 129.4 (CH), 129.6 (CH), 130.4 (C), 131.1 (CH), 149.2 (C),
165.1 (C=O), 169.4 (C=O). MS: m/z (%) = 284 (M+, 2), 269 (12),
238 (41), 166 (46), 143 (69), 141 (100). Anal. Calcd for C17H16O4
(284.31): C, 71.82; H, 5.67. Found: C, 72.34; H, 5.98.
(18) Sakamoto, R.; Inada, T.; Selvakumar, S.; Moteki, S. A.; Maruoka,
K. Chem. Commun. (Cambridge) 2016, 52, 3758.
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(20) Ghazanfarpour-Darjani, M.; Babapour-Kooshalshahi, M.;
Mousavi-Safavi, S. M.; Akbari-Neyestani, J.; Khalaj, M. Synlett
2016, 27, 259.
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Faraji Shamami, S. J. Sulfur Chem. 2016, 37, 211.
(22) Alkyl Arylalkenoates 3a–l; General Procedure
A sample tube was charged with TBAI (74 mg, 20 mol%), 70% aq
TBHP (2.0 mmol), and the appropriate alkyne 2 (1.0 mmol), and
the mixture was stirred for 15 min at 25 °C. The appropriate
toluene derivative 1 (1.5 mL) was added and the mixture was
stirred under vacuum at 80 °C for 14 h. The crude mixture was
then concentrated in vacuo, and the reaction was quenched by
addition of sat. aq Na2S2O3 (3.0 mL). The mixture was extracted
with EtOAc (3 × 5 mL), and the combined organic phases were
dried (MgSO4), filtered, and concentrated in vacuo. The crude
product was purified by column chromatography [silica gel,
hexane–EtOAc (8:1)].
Dimethyl 1H-Indene-2,3-dicarboxylate (4)
A mixture of fumarate 3c (1.0 mmol), Pd2dba3 (0.05 mmol),
tris(2-furyl)phosphine (0.15 mmol), and Cs2CO3 (3.0 mmol) in
1,4-dioxane (3.0 mL) was stirred for 30 min at 25 °C. The reac-
tion vessel was evacuated and back-flushed with N2 (3×), and
the mixture was stirred at 90 °C for 18 h. The mixture was then
diluted with EtOAc (5.0 mL), sat. aq NH4Cl (5.0 mL) was added,
and the resulting mixture was stirred for an additional 30 min.
The two layers were separated, and the aqueous layer was
extracted with EtOAc (3 × 5 mL). The organic layers were com-
bined, dried (MgSO4), filtered, and concentrated in vacuo. The
residue was purified by flash column chromatography [silica
gel, hexane–EtOAc (5:1)] to give a yellow oil; yield: 0.21 g (89%).
IR (KBr): 3028, 2957, 1735, 1728, 1371, 1107 cm–1 1H NMR
.
(500.1 MHz, CDCl3): δ = 3.57 (s, 3 H), 3.71 (s, 3 H), 4.11 (s, 2 H),
7.11 (d, 3J = 6.7 Hz, 1 H), 7.23–7.34 (m, 2 H), 7.57 (d, 3J = 7.1 Hz, 1
H). 13C NMR (125.7 MHz, CDCl3): δ = 46.2 (CH2), 53.0 (OCH3),
53.6 (OCH3), 125.3 (CH), 125.9 (CH), 126.5 (CH), 129.1 (CH),
130.3 (C), 133.5 (C), 142.3 (C), 147.8 (C), 165.5 (C=O), 167.1
(C=O). MS: m/z (%) = 232 (M+, 4), 173 (16), 114 (37), 91 (100), 77
(61). Anal. Calcd for C13H12O4 (232.24): C, 67.23; H, 5.21. Found:
C, 67.89; H, 5.76.
Dimethyl 2-Benzylfumarate (3a)
Colorless oil; yield: 0.17 g (84%). IR (KBr): 3035, 2928, 1728,
1715, 1311, 1108 cm–1; 1H NMR (500.1 MHz, CDCl3): δ = 3.57 (s,
© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–C