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Angewandte
Chemie
2003, 59, 7345 – 7355; < lit c > D. Iijima, D. Tanaka, M.
Hamada, T. Ogamino, Y. Ishikawa, S. Nishiyama, Tetrahedron
Lett. 2004, 45, 5469 – 5471.
Experimental Section
Benzaldehyde 2 (200 mg, 0.46 mmol) and [PdCl2(dppf)] (3.8 mg,
4.6 mmol, 1 mol%) were dissolved in absolute DMF (8 mL) under an
argon atmosphere. Allyltributylstannane (0.17 mL, 0.54 mmol) was
added to the reaction flask, and the resulting mixture was stirred at
1208C for 4 h. After the reaction mixture had cooled to RT, a
saturated aqueous solution of KF (10 mL) was added. After
extraction with MTBE (4 ꢀ 10 mL) the combined organic layers
were washed with brine (20 mL) and dried over MgSO4, and the
solvents were then evaporated. The residue was purified by flash
chromatography (SiO2, cyclohexane/EtOAc = 6:1) to give indanol 4
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through intramolecular Heck reaction of arene–Cr(CO)3 com-
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1
as an orange solid (111 mg, 0.32 mmol, 70%); H NMR: (250 MHz,
CDCl3): d = 2.72 (d, J = 17.5 Hz, 1H), 3.11 (dd, J = 17.5 Hz, 7.5 Hz,
1H), 3.46 (s, 3H), 3.49 (s, 3H), 5.13 (s, 1H), 5.20 (s, 2H), 5.23 (s, 2H),
5.23 (m, 1H), 5.81 (s, 1H), 6.91 ppm (s, 1H); 13C NMR: (75 MHz,
CDCl3): d = 41.2 (t), 56.2 (q), 56.5 (q), 73.5 (d), 94.3 (t), 95.5 (t), 101.9
(s), 103.5 (d), 108.6 (t), 124.7 (s), 144.3 (s), 148.6 (s), 154.1 (s),
154.3 ppm (s); MS: (EI, 70 eV): typical isotope pattern corresponding
to a molecule containing one bromine atom, m/z (%) = 346 (11,
[M(C14H17O581Br)]+), 344 (11, [M(C14H17O579Br)]+), 284 (10), 282
(12); HRMS: calc. for C14H17O579Br: 344.0259, found: 344.026.
Received: April 6, 2009
Published online: July 9, 2009
Keywords: allylation · domino reactions · Heck reaction ·
.
palladium · stannanes
[12] After aqueous extractive workup (MTBE) and removal of all
volatiles in vacuo, the crude triflates 14 were obtained with
ꢀ 95% purity (GC-MS).
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aldehyde species indicated by a singlet at d = 10.50 ppm in low
concentration besides the starting material 6 (10.25 ppm). The
assignments were supported by two-dimensional correlation
spectra. Species related to 17 have been structurally character-
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much more favorable than alternative pathways via allyl–
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ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
6151