G. de Gonzalo et al. / Tetrahedron 60 (2004) 10525–10532
10531
1448 and 1218 cmK1; 1H NMR (CDCl3, 200 MHz): d 1.45–
1.56 (m, 4H), 1.64–1.72 (m, 2H), 1.79–1.90 (m, 2H), 2.70
Found: C, 78.0; H, 6.6; N, 3.4; HPLC conditions: column
Chirobiotic T, eluent hexane/i-propanol (95:5),
0.3 mL minK1, 20 8C; tR (min): 29.40.
3
3
(d, 1H, JHHZ9.8 Hz), 3.10 (t, 2H, JHHZ6.3 Hz), 4.43 (t,
3
1H, JHHZ6.6 Hz), 7.22–7.37 (m, 9H) and 7.45–7.53 (m,
6H); 13C NMR (CDCl3, 50.4 MHz): d 24.4 (CH2), 25.7
(CH2), 29.8 (CH2), 35.2 (CH2), 61.3 (CH), 63.2 (CH2), 86.4
(C), 119.9 (C^N), 126.9 (CH), 127.8 (CH), 128.7 (CH) and
144.4 (C); MS (ESIC, m/z): 408 [(MCNa)C, 100] and 386
[(MCH)C, 3]. Anal. Calcd (%) for C26H27NO2: C, 81.01;
H, 7.06; N, 3.63. Found: C, 81.2; H, 7.0; N, 3.5; HPLC
conditions after acetylation: column Chirobiotic T, eluent
hexane/i-propanol (97:3), 0.3 mL minK1, 20 8C; tR (min):
24.68.
4.11.12. (S)-2-Acetoxy-6-trityloxyhexanenitrile, 4e.
Hygroscopic solid; [a]1D8ZK20.8 (c 0.95, MeOH; ee
95%); IR (KBr): n 3058, 2933, 2241, 1753, 1596, 1490
and 1219 cmK1; 1H NMR (CDCl3, 200 MHz): d 1.58–1.72
(m, 4H), 1.83–1.90 (m, 2H), 2.14 (s, 3H), 3.11 (t, 2H,
3
3JHHZ5.9 Hz), 5.31 (t, 1H, JHHZ6.7 Hz), 7.24–7.37 (m,
9H) and 7.41–7.52 (m, 6H); 13C NMR (CDCl3, 50.4 MHz):
d 20.5 (CH3), 21.5 (CH2), 29.1 (CH2), 32.1 (CH2), 61.0
(CH), 62.7 (CH2), 85.5 (C), 116.9 (C^N), 127.0 (CH),
127.8 (CH), 128.7 (CH), 144.2 (C) and 169.2 (C]O); MS
(ESIC, m/z): 452 [(MCK)C, 12] and 436 [(MCNa)C, 100].
Anal. Calcd (%) for C27H27NO2: C, 78.42; H, 6.58; N, 3.39.
Found: C, 78.2; H, 6.7; N, 3.3; HPLC conditions: column
Chiralcel OD, eluent hexane/i-propanol (98:2),
0.3 mL minK1, 20 8C; tR (min): 50.31.
4.11.8. (S)-2,5-Diacetoxypentanenitrile, 4a. Colourless
oil; [a]1D8ZK30.9 (c 0.90, MeOH; ee 75%); GC conditions:
column Rt-bDEXse, 1 mL minK1 N2, 100 8C, 5 min;
5 8C minK1 until 200 8C, tR (min): 22.83.
4.11.9. (S)-2-Acetoxy-5-benzoyloxypentanenitrile, 4b.
Colourless oil; [a]1D8ZK9.0 (c 0.83, MeOH; ee 59%); IR
(KBr): n 3020, 2942, 2246, 1753, 1714, 1622, 1454, and
4.11.13. (S)-2-Acetoxy-7-trityloxyheptanenitrile, 4f.
Hygroscopic solid; [a]1D8ZK21.2 (c 1.35, MeOH; ee
95%); IR (KBr): n 3022, 2938, 2240, 1752, 1597, 1448
and 1217 cmK1; 1H NMR (CDCl3, 200 MHz): d 1.46–1.52
(m, 4H), 1.62–1.70 (m, 2H), 1.85–1.92 (m, 2H), 2.11 (s,
3H), 3.09 (t, 2H, 3JHHZ6.2 Hz), 5.30 (t, 1H, 3JHHZ6.7 Hz),
7.21–7.36 (m, 9H) and 7.43–7.50 (m, 6H); 13C NMR
(CDCl3, 75.5 MHz): d 20.3 (CH3), 24.3 (CH2), 25.5 (CH2),
29.6 (CH2), 32.1 (CH2), 60.9 (CH), 63.0 (CH2), 86.2 (C),
116.8 (C^N), 126.9 (CH), 127.6 (CH), 128.6 (CH), 144.4
(C) and 169.1 (C]O); MS (ESIC, m/z): 450 [(MCNa)C,
100] and 438 [(MCH)C, 2]. Anal. Calcd (%) for
C28H29NO2: C, 81.72; H, 7.10; N, 3.40. Found: C, 81.5;
H, 7.2; N, 3.6; HPLC conditions: column Chirobiotic T,
eluent hexane/i-propanol (97:3), 0.3 mL minK1, 20 8C; tR
(min): 28.40.
1
1215 cmK1; H NMR (CDCl3, 300 MHz): d 1.93–2.05 (m,
3
2H), 2.07–2.16 (m, 2H), 2.19 (s, 3H), 4.41 (t, 2H, JHH
Z
3
3
6.0 Hz), 5.43 (t, 1H, JHHZ6.2 Hz), 7.48 (t, 2H, JHH
7.4 Hz), 7.60 (t, 1H, JHHZ7.4 Hz) and 8.06 (dd, 2H,
Z
3
4
3JHHZ7.4 Hz, JHHZ1.4 Hz); 13C NMR (CDCl3,
75.5 MHz): d 20.2 (CH3), 24.0 (CH2), 29.2 (CH2), 60.6
(CH), 63.4 (CH2), 116.4 (C^N), 128.3 (CH), 129.7 (CH),
129.8 (C), 130.1 (CH), 166.3 (C]O) and 169.0 (C]O); MS
(ESIC, m/z): 300 [(MCK)C, 21], 284 [(MCNa)C, 100] and
262 [(MCH)C, 5]. Anal. Calcd (%) for C14H15NO3: C,
64.36; H, 5.79; N, 5.36. Found: C, 64.5; H, 5.6; N, 5.4;
HPLC conditions: column Chiralcel OD, eluent hexane/
i-propanol (90:10), 0.8 mL minK1, 35 8C; tR (min): 16.98.
4.11.10. (S)-2-Acetoxy-5-(methoxy)methoxypentane-
nitrile, 4c. Colourless oil; [a]1D8ZK29.0 (c 0.94, MeOH;
ee 78%); IR (KBr): n 2947, 2251, 1752, 1436 and 1215 cmK1
;
Acknowledgements
1H NMR (CDCl3, 200 MHz): d 1.75–1.88 (m, 2H), 2.00–
2.11 (m, 2H), 2.16 (s, 3H), 3.37 (s, 3H), 3.59 (t, 2H, 3JHH
Z
This work has been supported by grants from MCYT
(Spain: Project PPQ-2001-2683) and the Principado de
Asturias (Spain: Project GE-EXP01-03). I. L. thanks MCYT
(Spain) for a pre-doctoral fellowship.
3
5.9 Hz), 4.62 (s, 2H) and 5.41 (t, 1H, JHHZ6.7 Hz); 13C
NMR (CDCl3, 75.5 MHz): d 19.9 (CH3), 24.3 (CH2), 29.1
(CH2), 54.8 (CH3), 60.4 (CH), 65.8 (CH2), 95.9 (CH2),
116.3 (C^N) and 168.7 (C]O); MS (ESIC, m/z): 224
[(MCNa)C, 100] and 202 [(MCH)C, 15]. Anal. Calcd (%)
for C9H15NO3: C, 53.72; H, 7.51; N, 6.96. Found: C, 53.7;
H, 7.4; N, 7.0; GC conditions: column Rt-bDEXse,
1 mL minK1 N2, 100 8C, 5 min; 5 8C minK1 until 200 8C,
tR (min): 21.52.
References and notes
1. North, M. Tetrahedron: Asymmetry 2003, 14, 147–176, and
references cited therein.
´
2. (a) Menendez, E.; Brieva, R.; Rebolledo, F.; Gotor, V.
4.11.11. (S)-2-Acetoxy-5-trityloxypentanenitrile, 4d.
Hygroscopic solid; [a]1D8ZK22.4 (c 1.28, MeOH; ee
96%); IR (KBr): n 3022, 2934, 2240, 1596, 1448 and
J. Chem. Soc., Chem. Commun. 1995, 989. (b) Monterde,
M. I.; Brieva, R.; Gotor, V. Tetrahedron: Asymmetry 2001, 12,
525–528.
1
1220 cmK1; H NMR (CDCl3, 200 MHz): d 1.78–1.84 (m,
3
2H), 1.97–2.07 (m, 2H), 2.14 (s, 3H), 3.17 (t, 2H, JHH
Z
6.0 Hz), 5.33 (t, 1H, 3JHHZ6.4 Hz), 7.26–7.37 (m, 9H) and
7.42–7.47 (m, 6H); 13C NMR (CDCl3, 50.4 MHz): d 20.8
(CH3), 25.1 (CH2), 29.5 (CH2), 60.9 (CH), 62.1 (CH2), 86.6
(C), 116.7 (C^N), 127.1 (CH), 127,8 (CH), 128.5 (CH),
143.9 (C) and 169.0 (C]O); MS (ESIC, m/z): 438 [(MC
K)C, 60], 422 [(MCNa)C, 100] and 400 [(MCH)C, 2].
Anal. Calcd (%) for C26H25NO2: C, 78.17; H, 6.31; N, 3.51.
3. De Gonzalo, G.; Brieva, R.; Gotor, V. J. Mol. Catal. B: Enzym.
2002, 19-20, 223–230.
4. Ognyanov, V. I.; Datcheva, K.; Kyler, K. S. J. Am. Chem. Soc.
1991, 113, 6992–6996.
5. Gregory, R. J. H. Chem. Rev. 1999, 99, 3649–3682. (b)
Griengl, H.; Schwab, H.; Fechter, M. TIBTECH 2000, 18,
425–429. (c) Brussee, J.; van der Gen, A. Patel, R. N., Eds.;