5
J. Tetrahedron Lett. 1997, 38, 1633. (c) Martin, R.; Romea, P.;
dried over MgSO4, filtered and concentrated under reduced
pressure. Purification of the residue by short column
chromatography on silica gel using Et2O yielded dodecanal (183
mg, 99%). All products in Table 6 were confirmed by
comparison with 1H NMR and GC data of authentic sample.
ACCEPTED MANUSCRIPT
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4.6 Preparation of LDBMA
3.
A dry and argon-flushed flask, equipped with a magnetic
stirring bar and a septum, was charged with methanol (2.23 mL,
55 mmol) and 25 mL THF. After cooling to 0 ℃, n-butyllithium
(20 mL, 2.5 M in hexane, 50 mmol) was added dropwise and
stirred for 1 hr at room temperature. To a reaction mixture was
slowly added DIBALH (50 mL, 1.0 M in hexane, 50 mmol) and
stirred for 2 h at same temperature to give a colorless
homogeneous solution. The concentration of LDBMA solution in
THF-hexane was measured gasometrically by hydrolysis of an
aliquot of the solution with a hydrolyzing mixture of t-butyl
alcohol-THF (1:1) at 0 ℃.
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4.7 Synthesis of N-benzyl-4-formylpiperidine (2)
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7. (a) Sugimoto, H; Tsuchiya, Y.; Sugumi, H.; Higurashi, K.; Karibe,
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S.; Yamanishi, Y.; Yamatsu, K. J. Med. Chem. 1990, 33, 1880. (b)
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2011, 3, 357.
A dry and argon-flushed flask, equipped with a magnetic
stirring bar and a septum, was charged with morpholine (0.18 mL,
2.1 mmol) and 10 mL THF. After cooling to 0 ℃, DIBALH (2.0
mL, 1.0 M in hexane, 2.0 mmol) was added dropwise and stirred
for 3 h at same temperature. To a reaction mixture was slowly
added ethyl N-benzylpiperidine-4-carboxylate (0.247 g, 1.0
mmol) and stirred for 10 min. Then, LDBMA (2.8 mL, 0.46 M in
hexane-THF, 1.3 mmol) was added and the mixture was stirred
for 10 min again. The reaction was stopped by the aqueous 1 N
HCl (10 mL) and extracted with diethyl ether (2 x 10 mL). The
combined organic layers were dried over MgSO4, filtered and
concentrated under reduced pressure. Purification of the residue
by column chromatography on silica gel yielded N-benzyl-4-
formylpiperidine (191 mg, 94%). The product was confirmed by
comparison with 1H NMR data reported in the literature.10
Acknowledgments
This research was supported by National Research Foundation
of Korea Grant funded by the Korean Government
(2012R1A1B6000451).
9. (a) Yoshida, J.; Itoh, M.; Matsunaga, S.; Isoe, S. J. Org. Chem.
1992, 57, 4877. (b) Fausett, B. W.; Liebeskind, L. S. J. Org.
Chem. Soc. 2005, 70, 4851. (c) Oh, C. H.; Kim, A.; Park, W.;
Park, D. I.; Kim, N. Synlett, 2006, 17, 2781. (d) James, J. J.;
Henderson, K. W.; Kerr, W. J. Org. Lett. 2006, 8, 5073. (e)
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References and notes
10. Abe, T.; Haga, T.; Negi, S.; Morita, Y.; Takayanagi, K.;
Hamamura, K. Tetrahedron 2001, 57, 2701.
1. Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815.
2. (a) Seki, M; Matsumoto, K. Tetrahedron Lett. 1996, 37, 3165. (b)
Martin, R.; Pascual, O.; Romea, P.; Rovira, R.; Urpi, F.; Vilarrasa,