O. Bondarev, C. Bruneau / Tetrahedron: Asymmetry 21 (2010) 1350–1354
1353
136.4, 135.9, 130.5, 129.6, 128.8, 128.7, 127.1, 126.1, 126.0, 53.6,
0.6 mL/min, tR1 11.8 min, tR2 12.5 min). ½a D22
ꢁ
¼ ꢀ2:4 (c 0.0075,
49.1, 36.9, 29.8, 28.1, 19.1; HRMS (ESI) calcd for C18H22N, [M+H]+
252.17522, found 252.1751; Anal. calcd for C18H21N: C, 86.01; H,
8.42; N, 5.57. Found: C, 85.40; H, 8.36; N, 5.10. Enantiomeric excess
was determined by chiral HPLC (Chiralpak AD column 254 mm,
4.6-mm ID, hexane/2-propanol (90:10), 0.6 mL/min, tR1 7.9 min,
CHCl3, for 6% ee material from entry 5, Table 3).
4.4. Typical procedure for the debenzylation of (ꢀ)-benzyl-
(1,2,3,4-tetrahydronaphthalen-2-yl)amine
tR2 8.6 min). ½a 2D2
ꢁ
¼ ꢀ7:6 (c 0.0112, CHCl3, for 29% ee material from
(ꢀ)-Benzyl-(1,2,3,4-tetrahydronaphthalen-2-yl)amine (237 mg,
1 mmol) (60% ee) was dissolved in absolute EtOH (10 mL), 10%
Pd/C catalyst (100 mg) was added, and the amine was debenzylat-
ed in a steel autoclave for 2 h at 45 °C under a H2 pressure of 5 bar.
After filtering off the catalyst, the volatiles were removed under re-
duced pressure to give a brown oil. The crude oil was purified by
flash chromatography (silica gel, eluting with CHCl3/MeOH/
iPrNH2 = 9:0.5:0.5) to yield 128 mg of (2S)-(1,2,3,4-tetra-
hydronaphthalen-2-yl)amine (0.87 mmol, 87% yield).
entry 3, Table 3).
4.3.4. (2,4-Dimethylbenzyl)-(1,2,3,4-tetrahydronaphthalen-2-
yl)amine
1H NMR (300 MHz, CDCl3) dY 7.26 (d, J = 6.0 Hz, 1H), 7.15 (m,
5H), 7.05 (m, 1H), 7.03 (d, J = 6.0 Hz, 1H), 3.91 (s, 2H), 3.14 (m,
2H), 2.97 (m, 2H), 2.75 (m, 1H), 2.41 (s, 3H), 2.36 (s, 3H), 2.17
(m, 1H), 1.71 (m, 1H), 1.69 (s, 1H); 13C NMR (75.5 MHz, CDCl3) dC
136.6, 136.5, 136.3, 135.9, 135.7, 131.3, 129.6, 128.8, 128.7,
126.0, 125.9, 125.8, 53.5 48.9, 36.9, 29.8, 28.2, 21.2, 19.1; HRMS
(ESI) calcd for C19H24N, [M+H]+ 266.19087, found 266.1915; Anal.
calcd for C19H23N: C, 85.99; H, 8.74; N, 5.28. Found: C, 86.35; H,
8.75; N, 4.89. Enantiomeric excess was determined by chiral HPLC
(Chiralpak AD column 254 mm, 4.6-mm ID, hexane/2-propanol
4.4.1. (2S)-(1,2,3,4-Tetrahydronaphthalen-2-yl)-amine15
½
a 2D2
ꢁ
¼ ꢀ51:2 (c 0.018, CHCl3, for 60% ee). 1H NMR (300 MHz,
CDCl3) dY 7.20–7.02 (m, 4H), 3.22 (m, 1H), 3.09 (dd, J = 16.2,
4.2 Hz, 1H), 2.91 (m, 2H), 2.62 (dd, J = 16.2, 9.4 Hz, 1H); 2.02 (m,
1H); 1.64 (m, 1H); 1.40 (s, 2H); 13C NMR (75.5 MHz, CDCl3) dC
135.9, 135.4, 129.3, 128.7, 125.8, 125.7, 47.4, 39.6, 33.0, 28.1;
HRMS (EI) calcd for C10H13N, [M]+ 147.1048, found 147.1052; Anal.
calcd for C10H13N: C, 81.59; H, 8.90; N, 9.51. Found: C, 81.65; H,
8.88; N, 9.47.
(95:5), 0.6 mL/min, tR1 8.5 min, tR2 9.0 min). ½a D22
¼ ꢀ18:5 (c
ꢁ
0.0183, CHCl3, for 45% ee material from entry 4, Table 3).
4.3.5. (4-Trifluoromethylbenzyl)-(1,2,3,4-tetrahydronaph-
thalen-2-yl)amine
Acknowledgement
1H NMR (300 MHz, CDCl3) dY 7.73 (dd, J = 37.2 Hz, J = 12.0 Hz,
4H), 7.26 (m, 4H), 4.08 (s, 2H), 3.15 (m, 2H), 3.01 (m, 2H), 2.87
(m, 1H), 2.18 (m, 2H), 1.83 (s, 1H); 13C NMR (75.5 MHz, CDCl3) dC
145.3, 136.7, 136.3, 135.6, 135.1, 129.9, 129.2, 128.9, 126.4,
126.3, 125.6 (q, J = 7.5 Hz), 53.4, 51.0, 37.2, 29.9, 28.4; 19F NMR
(282 MHz, CDCl3) dF ꢀ62.7 (s); HRMS (ESI) calcd for C18H19NF3,
[M+H]+ 306.14696, found 306.1467; Anal. calcd for C18H18NF3: C,
70.80; H, 5.94; N, 4.59. Found: C, 71.13; H, 6.04; N, 4.24. Enantio-
meric excess was determined by chiral HPLC (Chiralpak AD column
254 mm, 4.6-mm ID, hexane/2-propanol (95:5), 0.6 mL/min, tR1
Dr. O. Bondarev thanks the European Commission, 7th Frame-
work Programme for a Marie Curie fellowship, Grant Agreement
PIEF-GA-2008-221267.
References
1. Sheldon, R. A.; Arends, I.; Hanefeld, U. Green Chemistry and Catalysis; Wiley-
VCH: Weinheim, 2007.
2. (a) Nishimura, S. Handbook of Heterogeneous Catalytic Hydrogenation for Organic
Synthesis; Wiley: New York, 2001; (b) Fine Chemicals through Heterogeneous
Catalysis; Sheldon, A. S., van Bekkum, H., Eds.; Wiley-VCH: Weinheim, 2001; p
384.
9.1 min, tR2 10.3 min). ½a D22
¼ ꢀ22:3 (c 0.0153, CHCl3, for 40% ee
ꢁ
material from entry 1, Table 3).
3. (a) Kadyrov, R.; Riermeier, T. H.; Dingerdisson, U.; Tararov, V.; Börner, A. J. Org.
Chem. 2003, 68, 4067; (b) Tararov, V.; Börner, A. Synlett 2005, 203.
4. (a) Blaser, H.-U.; Buser, H.-P.; Jalett, H.-P.; Pugin, B.; Spindler, F. Synlett 1999,
867; (b) Chi, Y.; Zhou, Y.-G.; Zhang, X. J. Org. Chem. 2003, 68, 4120; (c) Zhang, X.
WO 2004/058982, 2004.
5. (a) Bunlaksananusorn, T.; Rampf, F. Synlett 2005, 2682; (b) Matsumara, K.;
Saito, K. WO 2005/028419, 2005.
6. (a) Boggs, S. D.; Cobb, J. D.; Gudmundsson, K. S.; Jones, L. A.; Matsuoka, R. T.;
Millar, A.; Patterson, D. E.; Samano, V.; Trone, M. D.; Xie, S.; Zhou, X. Org. Proc.
Res. Dev. 2007, 11, 539; (b) Williams, G. D.; Pike, R. A.; Wade, C. E.; Wills, M. Org.
Lett. 2003, 5, 4227.
7. Rubio-Perez, L.; Perez-Flores, J.; Sharma, P.; Velasco, L.; Cabrera, A. Org. Lett.
2009, 11, 265.
8. Zhou, J.; List, B. J. Am. Chem. Soc. 2007, 129, 7498; (a) Storer, R. I.; Carrera, D. E.;
Ni, Y.; MacMillan, D. W. C. J. Am. Chem. Soc 2006, 128, 84.
9. (a) Cordi, A.; Lacoste, J.-M.; Descombes, J.-J.; Courchay, C.; Vanhoutte, P.;
Laubie, M.; Verbeuren, T. J. Med. Chem. 1995, 38, 4056; (b) Duprat de Paule, S.;
Champion, N.; Ratovelomanana-Vidal, V; Genêt, J.P.; Dellis, P. FR 2830254
2001, WO 03029259, 2003.; (c) Dupau, P.; Bruneau, C.; Dixneuf, P. Adv. Synth.
Catal. 2001, 343, 331; (d) Renauld, J. L.; Dupau, P.; Hay, A.-E.; Guingouain, M.;
Dixneuf, P.; Bruneau, C. Adv. Synth. Catal. 2003, 345, 230.
4.3.6. (4-Methoxybenzyl)-(1,2,3,4-tetrahydronaphthalen-2-yl)-
amine
1H NMR (300 MHz, CDCl3) dY 7.37 (d, J = 6.0 Hz, 2H), 7.17 (m,
4H), 6.95 (d, J = 6.0 Hz, 2H), 3.92 (s, 2H), 3.86 (s, 3H), 3.14 (m,
2H), 3.07 (m, 2H), 2.74 (m, 1H), 2.13 (m, 1H), 1.76 (m, 1H), 1.54
(s, 1H); 13C NMR (75.5 MHz, CDCl3) dC 158.7, 136.4, 135.4, 132.8,
129.4, 129.3, 128.7, 125.8, 125.7, 113.9, 55.3, 52.8, 50.6, 36.8,
29.6, 28.1; HRMS (ESI) calcd for C18H22NO, [M+H]+ 268.17014,
found 268.1702; Anal. calcd for C18H21NO: C, 80.86; H, 7.92; N,
5.24. Found: C, 80.68; H, 7.60; N, 5.28. Enantiomeric excess was
determined by chiral HPLC (Chiralcel OJ column 254 mm, 4.6-
mm ID, hexane/2-propanol (95:5), 0.6 mL/min, tR1 27.8 min, tR2
29.6 min). ½a 2D2
¼ ꢀ31:05 (c 0.0033, CHCl3, for 43% ee material from
ꢁ
entry 2, Table 3).
10. Spindler, F.; Blaser, H.-U. Enantioselective hydrogenation of C@N
functions and enamines. In Handbook of Homogeneous Hydrogenation;
de Vries, J. G., Elsevier, C. J., Eds.; Wiley-VCH: Weinheim, 2007; Vol. 3,
pp 1193–1214.
11. (a) Tararov, V. I.; Kadyrov, R.; Riermeier, T. H.; Holz, J.; Börner, A. Tetrahedron
Lett. 2000, 41, 2351; (b) Hou, G.-H.; Xie, J.-H.; Wang, L.-X.; Zhou, Q.-L. J. Am.
Chem. Soc. 2006, 128, 11774; (c) Zhong, Y. L.; Krska, S. W.; Zhou, H.; Riermeier,
R. A.; Lee, J.; Sun, Y.; Askin, D. Org. Lett. 2009, 11, 369; (d) Hou, G.-H.; Xie, J.-H.;
Yan, P.-C.; Zhou, Q.-L. J. Am. Chem. Soc. 2009, 131, 1366; (e) Baeza, A.; Pfaltz, A.
Chem. Eur. J. 2009, 15, 2266.
4.3.7. (2,4,6-Trimethylbenzyl)-(1,2,3,4-tetrahydro-naphthalen-
2-yl)amine
1H NMR (300 MHz, CDCl3) dY 7.44 (m, 4H), 7.21 (s, 2H), 4.18 (s,
2H), 3.40 (m, 2H), 3.26 (m, 2H), 3.01 (m, 1H), 2.75 (s, 6H), 2.63 (s,
3H), 2.44 (m, 1H), 2.02 (m, 1H), 1.28 (s, 1H); 13C NMR (75.5 MHz,
CDCl3) dC 137.1, 136.6, 136.5, 135.8, 134.4, 129.7, 129.4, 129.0,
126.1, 126.0, 54.6, 45.6, 37.2, 30.1, 28.4, 21.3, 19.8; HRMS (ESI)
calcd for C20H26N, [M+H]+ 280.20653, found 280.2063; Anal. calcd
for C20H25N: C, 85.97; H, 9.02; N, 5.01. Found: C, 86.15; H, 8.72; N,
5.13. Enantiomeric excess was determined by chiral HPLC (Chiral-
cel OJ column 254 mm, 4.6-mm ID, hexane/2-propanol (95:5),
12. Iridium complexes: 1 [Ir(cod)Cl]2 + 4 (S)-(3,5-dioxa-4-phospha-cyclohepta[2,1-
a3,4-a0]dinaphthalen-4-yl)bis[(1S)-1-phenylethyl]amine;
2
iridium, [(11bS)-
N,N-bis[(1S)-1-phenylethyl]dinaphtho[2,1-d:10,20-f][1,3,2]dioxaphosphepin-4-
amine- P4][(1,2,5,6- )-1,5-cyclooctadiene][(2R)-2-[[(11bS)-dinaphtho[2,1-d:
10,20-f][1,3,2]dioxaphosphepin-4-yl-
P4][(1S)-1-phenylethyl]amino]-2-phen-
j
g
j