C. Pautigny et al. / Tetrahedron: Asymmetry 21 (2010) 1382–1388
1387
3J = 8.4 Hz, 1H), 8.15 (s, 1H). 13C NMR (75 MHz, CDCl3): d 25.8, 28.6,
References
35.8, 43.9, 55.3, 112.7, 113.9, 129.8, 134.7, 157.8, 160, 160.6. MS
(CI/NH3): m/z 223 ([M+NH4]+, 206 [M+H+]. HRMS calculated for
1. (a) Imanishi, M.; Tomishima, Y.; Itou, S.; Hamashima, H.; Nakajima, Y.;
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C12H15NO2Na: 214.09950, found: 214.09957. HPLC: Chiralcel OD-
H column, 215 nm UV detector, 85:15 hexane/iPrOH, flow rate
1 mL/min, tR (S) = 22 min, tR (R) = 26 min, 72% ee.
4.3.7. (R)-N-(7-Hydroxy-1,2,3,4-tetrahydro-naphthalen-2-yl)-
formamide 2g
Obtained as a beige solid (55 mg, 58% yield) after flash column
chromatography on silica gel (AcOEt/petroleum spirit 80/20); mp
175 °C. ½a 2D5
ꢂ
¼ þ45:6 (c 0.40, CHCl3). 1H NMR (300 MHz, CD3OD):
d 1.66–1.79 (m, 1H), 1.96–2.04 (m, 1H), 2.61 (dd, 2J = 16.3 Hz,
3J = 8.9 Hz, 1H), 2.76–2.80 (m, 2H), 2.96 (dd, 2J = 16.4 Hz,
3J = 5.2 Hz, 1H), 4.10–4.19 (m, 1H), 6.48 (d, 4J = 2.5 Hz, 1H), 6.55
(dd, 3J = 8.3 Hz, 4J = 2.6 Hz, 1H), 6.89 (d, 3J = 8.3 Hz, 1H), 8.01 (s,
1H). MS (CI/NH3): m/z 209 [M+NH4]+, 192 [M+H+]. HPLC: Chiralcel
OJ column, 215 nm UV detector, 90:10 hexane/iPrOH, flow rate
1 mL/min, tR (S) = 39.6 min, tR (R) = 50.7 min, 75% ee.
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4.4. General procedure for the deprotection of the N-acetyl
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Tone, H.; Lavergne, D.; Touati, R.; Ben Hassine, B.; Ratovelomanana-Vidal, V.;
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K.; Tadaoka, H.; Ayad, T.; Ohshima, T.; Genet, J.-P.; Mashima, K.;
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group and analytical data
A solution of acetamide (1.00 mmol) in dry THF (3 mL) was
treated with pyridine (0.100 mL, 1.20 mmol) and cooled to 0 °C.
The dropwise addition of oxalyl chloride (0.120 mL, 1.30 mmol)
was accompanied by vigorous bubbling and conversion of the
clear, colorless solution to a bright yellow slurry. After stirring at
0 °C for 30 min, dry propylene glycol (0.152 mL, 2.00 mmol) was
added in one portion and the reaction was warmed to room tem-
perature. Upon warming, the yellow slurry became lighter. The
mixture was treated with 1.1 mL of EtOH. After drying, 2 mL of
HCl 2 M in Et2O was added slowly. The resulting slurries were fil-
tered off and washed with MTBE. After drying, the desired com-
pound was recovered as a light yellow solid.
4.4.1. (S)-N-(7-Methoxy-1,2,3,4-tetrahydronaphthalen-2-yl)-
amine, hydrochloride 3a1e
Obtained as a white solid (144 mg, 66% yield). Mp 203 °C;
½
a 2D5
ꢂ
¼ ꢀ66:1 (c 0.5, MeOH). 1H NMR (300 MHz, CD3OD,): d 1.78–
1.86 (m, 1H), 2.17–2.23 (m, 1H), 2.77–2.90 (m, 3H, H1), 3.14 (dd,
2J = 16.1 Hz, 3J = 5.3 Hz, 1H), 3.49–3.54 (m, 1H), 3.75 (s, 3H), 6.67
(d, 4J = 2.3 Hz, 1H), 6.74 (dd, 3J = 8.6 Hz, 4J = 2.5 Hz, 1H), 7.04 (d,
3J = 8.5 Hz, 1H). 13C NMR (75 MHz, CD3OD): d 28.2, 29.6, 35.6,
48.7, 56.7, 115.1, 115.5, 128.6, 131.7, 135.2, 160.4. MS (CI/NH3)
m/z: 196 ([MꢀHCl+NH4]+), 178 ([MꢀHCl+H+]).
4.4.2. (S)-N-(7-Carbethoxymethoxy-1,2,3,4-tetrahydronaphth-
alen-2-yl)-amine hydrochloride 3b1e
Obtained as a white solid (194 mg, 68% yield). Mp 109 °C;
½
a 2D5
ꢂ
¼ ꢀ53:4 (c 1, MeOH). 1H NMR (300 MHz, CDCl3): d 1.30 (t,
14. Jiang, X.-B.; Lefort, L.; Goudrian, P. E.; de Vries, A. H. M.; de Vries, J. G.; Reek, J.
N. H. Angew. Chem., Int. Ed. 2006, 45, 1223.
15. Renaud, J. L.; Dupau, P.; Hay, A.-E.; Guingouain, M.; Dixneuf, P.-H.; Bruneau, C.
Adv. Synth. Catal. 2003, 345, 230.
16. Sala, X.; Serrano, I.; Rodriguez, M.; Romero, I.; Llobet, A.; Van Leeuwen, P. W. N.
M. Catal. Commun. 2008, 9, 117.
17. (a) Dupau, P.; Bruneau, C.; Dixneuf, P. H. Tetrahedron: Asymmetry 1999, 10,
3467; (b) Dupau, P.; Hay, A.-E.; Bruneau, C.; Dixneuf, P. H. Tetrahedron:
Asymmetry 2001, 12, 863.
3J = 7.1 Hz, 3H), 1.76–1.88 (m, 1H), 2.04–2.10 (m, 1H), 2.71 (dd,
2J = 16.2 Hz, 3J = 8.5 Hz, 1H), 2.85 (t, 3J = 6.5 Hz, 2H), 3.09 (dd,
2J = 16.5 Hz, 3J = 5.2 Hz, 1H), 4.15–4.28 (m, 1H), 4.27 (q,
3J = 7.1 Hz, 2H), 4.58 (s, 2H), 6.60 (d, 4J = 2.6 Hz, 1H), 6.72 (dd,
3J = 8.4 Hz, 4J = 2.7 Hz, 1H), 7.02 (d, 3J = 8.5 Hz, 1H), 7.49 (br d,
3J = 8.3 Hz, 1H). 13C NMR (75 MHz, CDCl3): d 13.9, 26.0, 28.3,
35.1, 45.5, 65.2, 113.0, 114.6, 128.1, 129.6, 134.5, 155.8, 159.0,
168.7. MS (CI/NH3): m/z 268 ([MꢀHCl+NH4]+), 250 ([MꢀHCl+H+]).
18. Jeulin, S.; Champion, N.; Dellis, P.; Ratovelomanana-Vidal, V.; Genet, J.-P.
Synthesis 2005, 20, 3666.
19. Genet, J.-P.; Pinel, C.; Ratovelomanana-Vidal, V.; Mallart, S.; Pfister, X.; Caño de
Andrade, M. C.; Laffitte, J. A. Tetrahedron: Asymmetry 1994, 5, 665.
20. Dobbs, D. A.; Vanhessche, K. P. M.; Brazi, E.; Rautenstrauch, V.; Lenoir, J. Y.;
Genet, J.-P.; Wiles, J. A.; Bergens, S. H. Angew. Chem., Int. Ed. 2000, 39, 1992.
21. For leading references see: (a) Togni, A. Angew. Chem., Int. Ed. 1996, 35, 1475;
(b) Vogl, E. M.; Groger, H.; Shibasaki, M. Angew. Chem., Int. Ed. 1999, 38, 1570;
(c) Spindler, F.; Blaser, H.-U. Enantiomer 1999, 4, 557; (d) Wang, W.-B.; Lu, S.-
M.; Yang, P.-Y.; Han, X.-W.; Zhou, Y.-G. J. Am. Chem. Soc. 2003, 125, 10536; (e)
Acknowledgments
We thank Sanofi-Aventis for a grant to C.P. We also thank the
Centre National de la Recherche Scientifique (CNRS) and the Min-
istère de l’Education et de la Recherche.