Dodd et al.
323
CDCl3 (unless otherwise noted) and referenced to residual
1H or 13C in the deuterated solvent. Coupling constants are
given in Hz. Elemental analyses were conducted by
Chemisar Laboratories Inc., Guelph, ON. Denaturing
polyacrylamide gels were cast and run according to litera-
ture procedures (22). The resultant gels were documented by
colour digital photography over fluorescent TLC plates illu-
minated at 258 nm. For clarity, the image presented has been
rendered in grayscale, inverted and contrast/brightness ad-
justed in Adobe Photoshop.
C15H14N2Cl2OPt: C, 35.73; H, 2.80; N, 5.56%. Found: C,
36.02; H, 2.76; N, 5.54%.
Dichloro-2-[(4S)-4-benzyl-4,5-dihydro-1,3-oxazol-2-
yl]pyridineplatinum(II) (S-2)
Yield: 68%. HRMS (ESI) calcd. for (M + Na)
C15H14N2Cl2ONaPt: 526.0029; found: 526.0041. Anal.
calcd. for C15H14N2Cl2OPt: C, 35.73; H, 2.80; N, 5.56%.
Found: C, 36.03; H, 3.06; N, 5.52%.
Dichloro-2-[(4R)-4-phenyl-4,5-dihydro-1,3-oxazol-2-
Optical rotations were recorded on an Atago Polax-2L
polarimeter at a concentration of 1 g /100 mL at 589 nm in
CH2Cl2 solution.
Stock solutions of the complexes (40 µmol/L) were pre-
pared by dissolution in a minimum amount of DMF
(<0.5 mL) followed by dilution with Milli-Q deionized wa-
ter to 100 mL and stored at RT in the dark for no longer than
2 weeks. DNA was purchased from the University of Cal-
gary DNA Services and used without further purification.
yl]pyridineplatinum(II) (R-3)
1
Yield: 94%. H NMR δ: 9.45 (m, 1H, py), 8.20 (m, 1H,
py), 7.86 (m, 1H, py), 7.62 (m, 1H, py), 7.38 (m, 5H, Ph),
2
3
5.88 (dd, 1H, CH2, J = 10.2, J = 4.9), 5.46 (dd, 1H, CH,
3J = 4.9, J = 3.8), 4.92 (dd, 1H, CH2, J = 10.2, J = 3.8).
13C{1H} NMR (CD2Cl2): δ: 174.3, 150.0, 149.6, 144.8,
139.5, 139.1, 130.3, 129.9, 129.1, 127.1, 126.8, 126.3, 81.1,
66.4. HRMS (ESI) calcd. for (M + Na) C14H12N2Cl2ONaPt:
511.9872; found: 511.9881. Anal. calcd. for C14H12N2Cl2OPt:
C, 34.30; H, 2.47; N, 5.71%. Found: C, 34.53; H, 2.72; N,
5.52%.
3
2
3
Syntheses
Dichloro-2-[(4R)-4-iso-propyl-4,5-dihydro-1,3-oxazol-2-
yl]pyridineplatinum(II) (R-1)
Dichloro-2-[(4S)-4-phenyl-4,5-dihydro-1,3-oxazol-2-
yl]pyridineplatinum(II) (S-3)
Yield: 92%. HRMS (ESI) calcd. for (M + Na)
C14H12N2ONaCl2Pt: 511.9872; found: 511.9869. Anal.
calcd. for C14H12N2Cl2OPt: C, 34.30; H, 2.47; N, 5.71%.
Found: C, 34.56; H, 2.75; N, 5.73%.
The title complex was synthesized by the addition of
cis/trans-PtCl2(SMe2)2 (0.23 g, 0.60 mmol) to 5 mL of 1,2-
dichloroethane containing a slight excess of pyridyl-
oxazoline ligand (0.14 g, 0.72 mmol). The resultant yellow
solution was heated to reflux for 4 h over which time it dark-
ened in colour. The solvent was removed in vacuo and the
remaining oil triturated with Et2O (10 mL). Vacuum filtra-
tion gave 0.27 g (94%) of R-1 as an orange/yellow powder.
Dichloro-2-[(4R)-4-iso-propyl-4,5-dihydro-1,3-oxazol-2-
yl]pyridinepalladium(II) (R-4)
The title complex was synthesized as described in the lit-
erature. Characterization data matched those of the known
compound (17).
1
[α] = –65.0°. H NMR δ: 9.51 (m, 1H, py), 8.17 (m, 1H,
py), 7.76 (m, 1H, py), 7.63 (m, 1H, py), 5.00 (m, 1H, CH2),
4.86 (m, 1H, CH), 4.71 (m, 1H, CH2), 2.99 (m, 1H, CH),
3
3
0.98 (d, 3H, CH3, J = 7.1), 0.83 (d, 3H, CH3, J = 6.9).
13C{1H} NMR δ: 173.2, 149.7, 145.0, 139.4, 129.4, 126.6,
73.3, 68.2, 28.9, 18.9, 14.1. HRMS (ESI) calcd. for (M +
Na) C11H14N2Cl2ONaPt: 477.0008; found: 477.0015. Anal.
calcd. for C11H14N2Cl2OPt: C, 28.96; H, 3.09; N, 6.14%.
Found: C, 28.90; H, 3.10; N, 6.21%.
Dichloro-2-[(4S)-4-iso-propyl-4,5-dihydro-1,3-oxazol-2-
yl]pyridinepalladium(II) (S-4)
The title complex was made in the same way as R-4.
Spectroscopic data matched those of the enantiomeric com-
pound.
Dichloro-2-[(4S)-4-sec-butyl-4,5-dihydro-1,3-oxazol-2-
yl]pyridineplatinum(II) (5)
Dichloro-2-[(4S)-4-iso-propyl-4,5-dihydro-1,3-oxazol-2-
yl]pyridineplatinum(II) (S-1)
Yield: 94%. [α] = 70.0°. (ESI) calcd. for (M + Na)
C11H14N2Cl2ONaPt: 477.0008; found: 476.9996. Orange
plates suitable for X-ray diffraction analysis were provided
by slow diffusion of Et2O into a CH2Cl2 solution of the title
complex.
Yield: 84%. 1HNMR δ: 9.26 (d, 1H, py, 3J = 5.5), 7.8 (dd,
3
3
3
1H, py, J = 5.5, J = 7.8), 7.76 (d, 1H, py, J = 7.6), 7.56
3
3
(dd, 1H, py, J = 7.8, J = 7.6), 5.13 (m, 1H, CH2), 4.87 (m,
1H, CH), 4.78 (m, 1H, CH2), 2.75 (m, 1H, CH), 1.29 (m,
2H, CH2), 1.00 (t, 3H, CH3, 3J = 7.4), 0.78 (d, 3H, CH3, 3J =
6.8). 13C{1H} NMR δ: 173.2, 149.8, 145.0, 139.3, 129.3,
126.5, 73.3, 66.9, 35.5, 26.5, 18.0, 11.9. HRMS (ESI) calcd.
for (M + Na) C12H16N2ONaCl2Pt: 492.0185; found: 492.0177.
Dichloro-2-[(4R)-4-benzyl-4,5-dihydro-1,3-oxazol-2-
yl]pyridineplatinum(II) (R-2)
1
Dichloro-2-[4,5-dihydro-1,3-oxazol-2-yl]pyridine-
platinum(II) (6)
Yield: 72%. H NMR δ: 9.63 (m, 1H, py), 8.15 (m, 1H,
py), 7.67 (m, 1H, py), 7.39 (m, 1H, py), 7.27 (m, 5H, Ar),
5.01 (m, 1H, CH2), 4.93 (m, 1H, CH), 4.85 (m, 1H, CH2),
The title compound has been previously made by a differ-
ent route (19). Following the procedure for R-1, 6 was ob-
tained in 72% yield. The limited solubility of this complex
did not allow for the measurement of NMR spectral data.
Anal. calcd. for C8H8N2Cl2OPt: C, 23.20; H, 1.95; N,
6.76%. Found: C, 23.50; H, 1.89; N, 6.66%.
2
3
3.66 (dd, 1H, CH2, J = 13.9, J = 10.7), 3.11 (dd, 1H, CH2,
2J = 13.9, J = 5.8). 13C{1H} NMR δ: 173.9, 150.1, 145.3,
139.7, 135.9, 130.2, 129.5, 129.2, 127.6, 126.8, 64.5, 39.8.
HRMS (ESI) calcd. for (M + Na) C15H14N2Cl2ONaPt:
3
526.0029;
found:
526.0008.
Anal.
calcd.
for
© 2008 NRC Canada