Organic & Biomolecular Chemistry
Paper
1H NMR (300 MHz, CDCl3) δ 8.27 (d, J = 9.2 Hz, 1H), 128.2, 128.0, 127.7, 127.0, 125.4, 125.0, 60.0, 51.5, 29.2, 21.3,
7.57–7.40 (m, 5H), 7.36–7.22 (m, 5H), 7.20–7.11 (m, 4H), 6.95 18.3.
(t, J = 7.5 Hz, 1H), 6.61 (d, J = 2.5 Hz, 1H), 5.94 (d, J = 7.8 Hz,
1H), 4.78 (s, 1H), 3.99–3.84 (m, 2H), 3.43 (dd, J = 8.0, 7.3 Hz, 520.0947.
HRMS: calc. for C26H25ClN3NiO3 [M + H]+ 520.0938, found
1H), 3.02 (d, J = 16.8 Hz, 1H), 2.05 (d, J = 6.9 Hz, 3H).
Ni(II) complexes of the Schiff’s base of 9 and DL-valine (14d)
13C NMR (75 MHz, CDCl3) δ 178.7, 177.6, 171.6, 141.5, and (15d). From 500 mg (1.27 mmol) of 9, 654 mg of a
138.5, 137.8, 133.5, 132.3, 132.1, 129.7, 129.0, 128.7, 128.6, 50 : 41 : 7 : 2 mixture of four diastereomers was obtained (yield:
128.6, 128.1, 128.0, 127.9, 127.6, 127.4, 126.9, 126.0, 125.6, 93.7%). A part of the mixture was subjected to column chromato-
125.1, 74.0, 61.2, 51.9, 21.8.
graphy to isolate diastereomerically pure products 14d (97 mg)
HRMS: calc. for C31H27ClN3NiO3 [M + H]+ 582.1094, found and 15d (74 mg) for full analytical characterization.
Data for 14d. Rf: 0.45 (CH2Cl2–acetone, 2 : 1). [α]2D5 = −2638
582.1097.
Data for 15b. Rf: 0.34 (CH2Cl2–acetone, 2 : 1). [α]2D5 = +2494 (c = 0.048, CHCl3).
(c = 0.031, CHCl3).
1H NMR (300 MHz, CDCl3) δ 8.24 (d, J = 9.2 Hz, 1H),
1H NMR (300 MHz, CDCl3) δ 8.11 (d, J = 9.2 Hz, 1H), 7.66 7.52–7.38 (m, 5H), 7.32–7.18 (m, 4H), 7.14 (dd, J = 9.2, 2.5 Hz,
(d, J = 7.0 Hz, 2H), 7.60 (dd, J = 6.3, 3.1 Hz, 2H), 7.46 (t, J = 1H), 6.85 (d, J = 7.2 Hz, 1H), 6.62 (d, J = 2.5 Hz, 1H), 3.98 (dd,
7.4 Hz, 1H), 7.36–7.17 (m, 8H), 7.10 (dd, J = 9.2, 2.6 Hz, 1H), J = 16.8, 6.5 Hz, 1H), 3.91–3.74 (m, 2H), 3.63 (dd, J = 8.2,
6.94 (t, J = 7.4 Hz, 1H), 6.59 (d, J = 2.6 Hz, 1H), 5.95 (d, J = 6.9 Hz, 1H), 3.01 (d, J = 16.8 Hz, 1H), 2.00 (d, J = 6.2 Hz, 3H),
7.8 Hz, 1H), 4.74 (s, 1H), 3.95 (qd, J = 7.0, 2.5 Hz, 1H), 3.64 1.97 (d, J = 6.3 Hz, 3H), 1.79–1.61 (m, 1H), 0.76 (d, J = 6.9 Hz,
(dd, J = 7.7, 2.1 Hz, 1H), 3.54 (dd, J = 17.0, 7.9 Hz, 1H), 3.03 3H).
(d, J = 16.9 Hz, 1H), 1.95 (d, J = 7.0 Hz, 3H).
13C NMR (75 MHz, CDCl3) δ 177.9, 176.7, 169.6, 141.4,
13C NMR (75 MHz, CDCl3) δ 178.7, 178.5, 171.5, 141.5, 138.5, 133.1, 132.3, 132.2, 130.1, 129.2, 129.1, 128.7, 128.5,
138.1, 138.0, 133.5, 132.2, 132.0, 129.7, 128.8, 128.6, 128.6, 128.0, 127.5, 127.1, 125.5, 124.8, 74.8, 61.2, 52.3, 34.2, 22.0,
128.3, 127.7, 127.3, 126.8, 126.0, 125.4, 125.2, 74.1, 61.1, 52.4, 19.7, 18.2.
18.8.
HRMS: calc. for C28H29ClN3NiO3 [M + H]+ 548.1251, found
HRMS: calc. for C31H27ClN3NiO3 [M + H]+ 582.1094, found 548.1253.
Data for 15d. Rf: 0.30 (CH2Cl2–acetone, 2 : 1). [α]2D5 = +2900
(c = 0.021, CHCl3).
582.1097.
Ni(II) complexes of the Schiff’s base of 9 and DL-alanine (14c)
and (15c). From 500 mg (1.27 mmol) of 9, 629 mg of a
48 : 42 : 7 : 3 mixture of four diastereomers was obtained (yield:
94.9%), Part of the mixture was subjected to column chromato-
graphy to isolate diastereomerically pure products 14c (43 mg)
and 15c (22 mg) for full analytical characterization.
1H NMR (300 MHz, CDCl3) δ 8.02 (d, J = 9.2 Hz, 1H), 7.72
(d, J = 7.0 Hz, 2H), 7.51–7.38 (m, 3H), 7.28–7.14 (m, 4H), 7.07
(dd, J = 9.2, 2.6 Hz, 1H), 6.84 (d, J = 7.2 Hz, 1H), 6.60 (d, J =
2.5 Hz, 1H), 3.94–3.69 (m, 4H), 3.12 (d, J = 16.5 Hz, 1H), 1.98
(d, J = 6.8 Hz, 3H), 1.86 (d, J = 7.0 Hz, 3H), 1.77–1.65 (m, 1H),
Data for 14c. Rf: 0.42 (CH2Cl2–acetone, 1 : 1). [α]2D5 = −3075 0.75 (d, J = 6.9 Hz, 3H).
(c = 0.050, CHCl3).
13C NMR (75 MHz, CDCl3) δ 178.1, 177.6, 169.5, 141.3,
1H NMR (300 MHz, CDCl3) δ 8.29 (d, J = 9.2 Hz, 1H), 138.0, 133.1, 132.2, 132.1, 130.1, 129.2, 129.1, 128.8, 128.5,
7.53–7.40 (m, 3H), 7.39–7.21 (m, 6H), 7.16 (dd, J = 9.2, 2.6 Hz, 128.3, 128.0, 127.1, 125.4, 124.8, 75.0, 61.3, 52.8, 34.2, 19.8,
1H), 6.89 (d, J = 7.1 Hz, 1H), 6.61 (d, J = 2.5 Hz, 1H), 4.08–3.74 18.7, 18.3.
(m, 3H), 3.25 (dd, J = 8.9, 6.8 Hz, 1H), 3.01 (d, J = 16.7 Hz, 1H),
2.04 (d, J = 6.9 Hz, 3H), 1.45 (d, J = 7.1 Hz, 3H).
HRMS: calc. for C28H29ClN3NiO3 [M + H]+ 548.1251, found
548.1255.
Ni(II) complexes of the Schiff’s base of 9 and DL-leucine (14e)
13C NMR (75 MHz, CDCl3) δ 181.1, 177.2, 169.8, 141.2,
138.7, 132.9, 132.2, 130.2, 129.3, 129.1, 128.8, 128.7, 128.1, and (15e). From 500 mg (1.27 mmol) of 9, 670 mg of a
127.9, 127.7, 127.4, 126.9, 125.6, 125.1, 65.9, 61.3, 52.2, 22.2, 51 : 40 : 7 : 2 mixture of four diastereomers was obtained (yield:
21.2.
93.6%). A part of the mixture was subjected to column chromato-
HRMS: calc. for C26H25ClN3NiO3 [M + H]+ 520.0938, found graphy to isolate diastereomerically pure products 14e (91 mg)
520.0949.
and 15e (77 mg) for full analytical characterization.
Data for 14e. Rf: 0.57 (CH2Cl2–acetone, 2 : 1). [α]2D5 = −2126
(c = 0.049, CHCl3).
Data for 15c. Rf: 0.24 (CH2Cl2–acetone, 1 : 1). [α]2D5 = +2669
(c = 0.050, CHCl3).
1H NMR (300 MHz, CDCl3) δ 8.21 (d, J = 9.2 Hz, 1H), 7.58
1H NMR (300 MHz, CDCl3) δ 8.22 (d, J = 9.2 Hz, 1H),
(d, J = 7.0 Hz, 2H), 7.54–7.36 (m, 3H), 7.34–7.20 (m, 4H), 7.11 7.54–7.33 (m, 5H), 7.33–7.17 (m, 4H), 7.13 (dd, J = 9.2, 2.5 Hz,
(dd, J = 9.2, 2.6 Hz, 1H), 6.89 (d, J = 7.2 Hz, 1H), 6.59 (d, J = 1H), 6.86 (d, J = 6.9 Hz, 1H), 6.61 (d, J = 2.4 Hz, 1H), 3.95 (dd,
2.5 Hz, 1H), 4.03 (qd, J = 6.9, 2.6 Hz, 1H), 3.90 (q, J = 7.1 Hz, J = 16.7, 6.6 Hz, 1H), 3.90–3.80 (m, 2H), 3.42 (t, J = 7.6 Hz, 1H),
1H), 3.72 (dd, J = 17.2, 8.0 Hz, 1H), 3.32 (d, J = 6.9 Hz, 1H), 3.01 (d, J = 16.8 Hz, 1H), 2.28 (ddd, J = 12.1, 10.3, 3.4 Hz, 1H),
3.12 (d, J = 17.5 Hz, 1H), 1.95 (d, J = 7.1 Hz, 3H), 1.44 (d, J = 1.99 (d, J = 6.9 Hz, 3H), 1.85 (br, 1H), 1.31–1.18 (m, 1H), 0.82
7.1 Hz, 3H).
13C NMR (75 MHz, CDCl3) δ 181.3, 178.5, 169.8, 141.3,
(d, J = 6.7 Hz, 3H), 0.38 (d, J = 6.4 Hz, 3H).
13C NMR (75 MHz, CDCl3) δ 179.7, 176.7, 169.2, 141.2,
137.9, 133.0, 132.2, 132.1, 130.2, 129.3, 129.1, 128.8, 128.7, 138.6, 133.0, 132.3, 130.3, 129.2, 129.0, 128.8, 128.5, 128.3,
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Org. Biomol. Chem., 2014, 12, 6239–6249 | 6245