Y. N. Belokon et al. / Tetrahedron: Asymmetry 19 (2008) 822–831
829
Val); 2.57–2.62 (m, 2H, b-CH-Val); 4.20 (d, J 8.1 Hz, 2H,
a-CH-Val); 6.60 (t, J 7.8 Hz, 2H, CHAr); 6.77 (d, J
13.2 Hz, 2H, CHAr); 7.09 (d, J 8.1 Hz, 2H, CHAr); 7.43
(d, J 11.7 Hz, 2H, CHAr); 8.40 (s, 2H, CH@N). Anal. Calcd
for C24H26CoKN2O6ꢁ2H2O: C, 50.35; H, 5.28; N, 4.89.
Found: C, 50.65; H, 4.80; N, 5.11.
(d, J 7.1 Hz, 2H, CHAr); 8.48 (s, 2H, CH@N). Anal. Calcd
for C24H26N2O6CoAgꢁ0.5H2O: C, 46.93; H, 4.43; N, 4.56.
Found: C, 46.90; H, 4.26; N, 4.33.
4.11. Potassium D-bis-[N-salicylidene-(S)-threoninato]-
cobaltate [D-2]K
25
4.6. Potassium D-bis-[N-salicylidene-(S)-valinato]-cobaltate
[D-1]K
70% yield. Mp >300 °C, ½aꢄD ¼ ꢀ5995 (c 0.0022, MeOH).
1H NMR (300 MHz, D2O): d 1.30 (d, J 8.7 Hz, 6H, CH3-
Thr); 4.19–4.21 (m, 2H, b-CH-Thr); 4.51 (d, J 8.1 Hz,
2H, a-CH-Thr); 6.58–6.60 (m, 4H, CHAr); 7.20 (t, J
9.6 Hz, 2H, CHAr); 7.50 (d, J 9.9 Hz, 2H, CHAr); 8.60 (s,
2H, CH@N). Anal. Calcd for C22H22CoKN2O8ꢁ2EtOH:
C, 50.91; H, 5.80; N, 4.24. Found: C, 50.80; H, 5.67; N,
4.59.
25
86% yield. Mp >300 °C, ½aꢄD ¼ ꢀ3630 (c 0.030, MeOH).
1H NMR (300 MHz, D2O): d 1.26–1.31 (m, 12H, CH3-
Val); 2.60–2.66 (m, 2H, b-CH-Val); 4.53 (d, J 8.0 Hz, 2H,
a-CH-Val); 6.53–6.61 (m, 4H, CHAr); 6.97 (t, J 10.2 Hz,
2H, CHAr); 7.47 (d, J 7.1 Hz, 2H, CHAr); 8.48 (s, 2H,
CH@N). Anal. Calcd for C24H26CoKN2O6ꢁ0.16C6H6: C,
54.64; H, 4.95; N, 5.10. Found: C, 54.61; H, 5.15; N, 5.09.
4.12. Sodium D-bis-[N-salicylidene-(S)-threoninato]-cobal-
tate ([D-2]Na)
4.7. Sodium K-bis-[N-salicylidene-(S)-valinato]-cobaltate
[K-1]Na
25
75% yield. Mp >300 °C. ½aꢄD ¼ ꢀ6405 (c 0.025, MeOH).
1H NMR (300 MHz, D2O): d 1.30 (d, J 8.7 Hz, 6H, CH3-
Thr), 4.21 (t, J 9.0 Hz, b-CH-Thr), 4.49 (d, J 8.2 Hz, 2H,
a-CH-Thr), 6.58–6.62 (m, 4H, CHAr), 7.18 (t, J 9.6 Hz,
2H, CHAr), 7.53 (d, J 9.9 Hz, 2H, CHAr), 8.62 (s, 2H,
CH@N). Anal. Calcd for C22H22N2O8CoNaꢁH2Oꢁ1/3
C6H6: C, 50.71; H, 4.61; N, 4.93. Found: C, 50.80; H,
4.67; N, 4.59.
25
87% yield. Mp >300 °C. ½aꢄD ¼ ꢀ6185 (c 0.031, MeOH);
1H NMR (300 MHz, CD3OD): d 1.21–1.31 (m, 12H,
CH3-Val); 2.57–2.67 (m, 2H, b-CH-Val); 4.31 (d, J
8.1 Hz, 2H, a-CH-Val); 6.60 (t, J 7.8 Hz, 2H, CHAr); 6.81
(d, J 13.2 Hz, 2H, CHAr); 7.09 (d, J 8.1 Hz, 2H, CHAr);
7.43 (d, J 11.7 Hz, 2H, CHAr); 8.39 (s, 2H, CH@N). Anal.
Calcd for C24H26N2O6CoNaꢁ0.75EtOHꢁ0.5H2O: C, 54.31;
H, 5.63; N, 4.97. Found: C, 54.34; H, 5.14; N, 4.64.
4.13. Silver D-bis-[N-salicylidene-(S)-threoninato]-cobaltate
[D-2]Ag
4.8. Sodium D-bis-[N-salicylidene-(S)-valinato]-cobaltate
([D-1]Na)
25
83% yield. Mp >300 °C. ½aꢄD ¼ ꢀ5978 (c 0.031 MeOH). 1H
NMR (300 MHz, D2O): d 1.53 (d, J 5.4 Hz, 6H, CH3-Thr);
4.34–4.47 (m, 2H, b-CH-Thr); 4.53–4.78 (m, 2H, a-CH-
Thr); 6.69 (t, J 7.35 Hz, 2H, CHAr); 6.84 (d, J 8.4 Hz,
2H, CHAr); 7.18 (t, J 7.8 Hz, 2H, CHAr); 7.54 (d, J
7.5 Hz, 2H, CHAr); 8.49 (s, 2H, CH@N). Anal. Calcd for
C22H22AgCoN2O8: C, 43.48; H, 3.74; N, 4.69. Found: C,
43.37; H, 3.64; N, 4.60.
25
84% yield. Mp >300 °C. ½aꢄD ¼ ꢀ3660 (c 0.034, MeOH).
1H NMR (300 MHz, CD3OD): d 1.26–1.31 (m, 12H,
CH3-Val); 2.60–2.66 (m, 2H, b-CH-Val); 4.53 (d, J
8.0 Hz, 2H, a-CH-Val); 6.53–6.61 (m, 4H, CHAr); 6.97 (t,
J 10.2 Hz, 2H, CHAr); 7.47 (d, J 7.1 Hz, 2H, CHAr); 8.48
(s, 2H, CH@N). Anal. Calcd for C24H26N2O6CoNaꢁ
0.5H2O: C, 54.45; H, 5.14; N, 5.29. Found: C, 54.42; H,
5.46; N, 5.46.
4.14. Potassium K-bis-[N-salicylidene-(S)-tryptophanato]-
cobaltate [K-3]K
4.9. Silver K-bis-[N-salicylidene-(S)-valinato]-cobaltate
[K-1]Ag
25
25
86% yield. Mp >300 °C, ½aꢄD ¼ ꢀ4060, ½aꢄ578 ¼ ꢀ3740,
25
½aꢄ546 ¼ ꢀ738 (c 0.032, MeOH). 1H NMR (300 MHz,
25
83% yield. Mp >300 °C. ½aꢄD ¼ ꢀ5600 (c 0.029 MeOH). 1H
D2O + CD3COCD3 (1:1)): d 3.14, 3.41 (AB part of ABX
system, JAB 14.0 Hz, JAX 8.4 Hz, JBX 11.4 Hz, 4H, CH2-
Trp); 4.81–4.84 (m, X part of ABX system, 2H, a-H-
Trp); 6.03 (d, J 8.0 Hz, 2H, CHAr); 6.15 (s, 2H, CHAr);
6.50 (d, J 9.0 Hz, 2H, CHAr); 6.68 (s, 2H, CHAr); 6.90 (s,
2H, CHAr); 6.97 (s, 4H, CHAr); 7.26 (d, J 7.4 Hz, 2H,
CHAr); 7.43 (d, J 7.2 Hz, 2H, CHAr); 7.83 (s, 2H, CH@N).
Anal. Calcd for C36H28CoKN4O6ꢁEt2O: C, 61.22; H, 4.88;
N, 7.14. Found: C, 61.53; H, 4.74; N, 7.57.
NMR (300 MHz, CD3OD): d 1.19–1.29 (m, 12H, CH3-
Val); 2.50–2.68 (m, 2H, b-CH-Val); 4.30 (d, J 8.1 Hz, 2H,
a-CH-Val); 6.57 (t, J 7.8 Hz, 2H, CHAr); 6.77 (d, J
13.2 Hz, 2H, CHAr); 7.08 (t, J 7.65 Hz, 2H, CHAr); 7.46
(d, J 7.8 Hz, 2H, CHAr); 8.39 (s, 2H, CH@N). Anal. Calcd
for C24H26N2O6CoAg: C, 47.62; H, 4.33; N, 4.63. Found:
C, 47.43; H, 4.41; N, 4.30.
4.10. Silver D-bis-[N-salicylidene-(S)-valinato]-cobaltate
[D-1]Ag
4.15. Potassium D-bis-[N-salicylidene-(S)-tryptophanato]-
cobaltate [D-3]K
25
81% yield. Mp >300 °C. ½aꢄD ¼ ꢀ2770 (c 0.026 MeOH). 1H
25
25
NMR (300 MHz, CD3OD): d 1.26–1.31 (m, 12H, CH3-
Val), 2.61–2.66 (m, 2H, b-CH-Val); 4.53 (d, J 8.0 Hz, 2H,
a-CH-Val); 6.61 (t, J 7.2 Hz, 2H, CHAr); 6.82 (d, J
8.4 Hz, 2H, CHAr); 6.97 (t, J 10.2 Hz, 2H, CHAr); 7.47
80% yield. Mp >300 °C, ½aꢄD ¼ ꢀ5280, ½aꢄ578 ¼ ꢀ5510,
25
½aꢄ546 ¼ ꢀ4890 (c 0.032, MeOH). 1H NMR (400 MHz,
D2O + CD3COCD3 (1:1)): d 3.14, 3.40 (AB part of
ABX system, JAB 13.2 Hz, JAX 9.2 Hz, JBX 12.8 Hz, 4H,