PAPER
Domino Approach to Dihydroisobenzofurans
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3.17 (s, 3 H, CH3), 5.01 (t, J = 7.3 Hz, 1 H, =CHCH2), 6.19 [s, 1 H,
CH(OCH3)O], 6.89–7.17 (m, 4 H, ArH).
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González, J. M. J. Am. Chem. Soc. 2003, 125, 9028.
(b) Barluenga, J.; Vásquez-Villa, H.; Merino, I.; Ballesteros,
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D.; Cà, N. D.; Larock, R. C. J. Org. Chem. 2006, 71, 3381.
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1581.
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Wu, M.-J. Synlett 2004, 1497. (b) Asao, N.; Nogami, T.;
Takahashi, K.; Yamamoto, Y. J. Am. Chem. Soc. 2002, 124,
764. (c) For copper, see: Patil, N. T.; Yamamoto, Y. J. Org.
Chem. 2004, 69, 5139. (d) For copper–palladium, see: Asao,
N.; Chan, C. S.; Takahashi, K.; Yamamoto, Y. Tetrahedron
2005, 61, 11322. For silver, see: (e) Godet, T.; Vaxelaire,
C.; Michel, C.; Milet, A.; Belmont, P. Chem. Eur. J. 2007,
13, 5632. (f) Yu, X.; Ding, Q.; Wang, W.; Wu, J.
Tetrahedron Lett. 2008, 49, 4390. (g) For gold, see: Yao,
X.; Li, C.-J. Org. Lett. 2006, 8, 1953. (h) For indium, see:
Obika, S.; Kono, H.; Yasui, Y.; Yanada, R.; Takemoto, Y.
J. Org. Chem. 2007, 72, 4462.
13C NMR (50.3 MHz, C6D6): d = 14.2, 22.8, 25.5, 29.9, 31.8, 53.5,
98.3, 106.3, 119.4, 123.3, 128.1, 129.5, 135.3, 137.9, 153.1.
ESI-MS: m/z (%) = 233 (100) [M + 1]+, 217 (25) [M – CH3]+, 201
(20) [M – OCH3]+.
(Z)-1-Methoxy-3-octylidene-1,3-dihydroisobenzofuran (2l) and
3-Heptyl-1-methoxy-1H-isochromene (3l)
The minor product 3l was identified only by 1H NMR analysis of the
crude reaction mixture [selected significant signals: 1H NMR (200
MHz, C6D6): = 3.27 (s, 3 H, CHd3), 5.65 (s, 1 H, CH), 5.82 (s, 1 H,
CH)]. Column chromatography (cyclohexane–EtOAc–Et3N,
99.2:0.2:0.6) of the crude material gave only 2l; compound 3l prob-
ably decomposed.
Yield: 94 mg (83%); yellow oil.
IR (neat, NaCl): 2955, 2925, 2854, 1687, 1467, 1371, 1113, 1092,
1007, 973, 753 cm–1.
1H NMR (200 MHz, C6D6): d = 0.85 (t, J = 7.0 Hz, 3 H, CH2CH3),
1.27–1.52 (m, 12 H, CH2), 2.52 (dt, J = 7.3, 7.3 Hz, 2 H, =CHCH2),
3.18 (s, 3 H, CH3), 5.04 (t, J = 7.3 Hz, 1 H, =CHCH2), 6.20 [s, 1 H,
CH(OCH3)O], 6.84–7.20 (m, 4 H, ArH).
13C NMR (50.3 MHz, C6D6): d = 14.2, 22.9, 25.6, 29.6, 29.7, 29.8,
30.3, 32.2, 53.5, 98.3, 106.3, 119.4, 123.3, 128.1, 129.5, 135.3,
137.9, 153.1.
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Lett. 1975, 50, 4467. (b) For a recent review, see:
Chinchilla, R.; Nájera, C. Chem. Rev. 2007, 107, 874.
(14) Lu, D. L.; Lin, C.-F.; Wang, C.-J.; Wang, S.-J.; Wu, M.-J.
Tetrahedron 2002, 58, 7315.
ESI-MS: m/z (%) = 275 (100) [M + 1]+.
References
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literature data, and confirmed by NOE experiments on
compounds 2d, 2i and 2j; the assignment was extended by
analogy to the entire series.
(21) These compounds are acid-sensitive. Their stability also
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(22) The same behaviour was observed by Belmont and co-
workers for the related compound 2-[(trimethylsilyl)ethyn-
yl]quinoline-3-carbaldehyde (see ref. 10a). In that paper, the
authors also demonstrated that, under basic conditions, the
desilylation occurred before the cyclisation step.
Synthesis 2010, No. 14, 2367–2378 © Thieme Stuttgart · New York