Á
O. Pamies et al. / Tetrahedron: Asymmetry 11 (2000) 1097±1108
1105
2H, CH2), 3.27 (dd, 1H, H-2, J2±1=3.3 Hz, J2±3=3.0 Hz), 3.49 (m, 1H, H-50), 3.81 (s, 12H,
OMe), 3.92 (m, 1H, H-5), 4.42 (m, 2H, H-3, H-4), 5.18 (m, 1H, CH), 5.41 (m, 1H, CH), 5.43
(d, 1H, H-1, 3J1±2=3.3 Hz), 6.20 (m, 1H, CH), 6.29 (m, 1H, CH), 6.60 (m, 2H, CH, arom),
6.69 (m, 1H, CH, arom.), 6.74 (m, 1H, CH, arom.), 7.04 (m, 4H, CH, arom.). 13C NMR
3
3
t
(CDCl3), ꢀ (ppm): 25.5 (CH3), 26.3 (CH3), 27.7 (CH2), 28.5 (CH2), 32.0 (CH3, Bu), 32.1 (CH3,
t
t
t
t
tBu), 32.2 (CH3, Bu), 35.3 (C, Bu), 35.4 (C, Bu), 35.6 (C, Bu), 55.7 (OCH3), 69.8 (dd, C-5,
JP±C=9.7 Hz, JP±C=3.5 Hz), 71.2 (t, C-4, JP±C=4.0 Hz), 77.0 (C-2), 77.3 (dd, C-3, JP±C=5.1 Hz,
JP±C=2.8 Hz), 101.5 (m, CH), 102.8 (m, CH), 103.1 (C-1), 109.7 (m, CH), 112.9 (CH),
113.2 (CMe2), 113.7, 114.3, 114.7, 115.5, 115.9 (CH), 128.0, 131.3, 131.9 (C), 132.4 (CH),
141.9, 142.3, 142.9, 156.5, 156.7, 157.3 (C).
3.2.1.3. [Rh(cod)(6)]BF4 9. 120 mg (88%, yellow solid). Elemental analysis. Found (%): C,
.
62.36; H, 7.57. Calculated (%) for C72H104BF4O9P2Rh 1/2CH2Cl2: C, 61.91; H, 7.52. FAB
spectrometry: m/z: 1277 [M+]. 31P NMR (CDCl3), ꢀ (ppm): 122.7 (dd, 1P, 2JP±P=26.7 Hz, 1JP±Rh
266.6 Hz), 123.6 (dd, 1P, 2JP±P=26.7 Hz, 1JP±Rh=265.3 Hz). 1H NMR (CDCl3), ꢀ (ppm): 1.11 (s,
=
t
t
t
3H, CH3), 1.37 (m, 39H, CH3, CH3 Bu), 1.48 (m, 18H, CH3 Bu), 1.62 (m, 18H, CH3 Bu), 1.81
(m, 2H, CH2), 2.20 (m, 2H, CH2), 2.45 (m, 2H, CH2), 2.62 (m, 2H, CH2), 3.21 (dd, 1H, H-2,
3J2±1=2.7 Hz, 3J2±3=2.4 Hz), 3.48 (m, 1H, H-50), 3.92 (m, 1H, H-5), 4.44 (m, 2H, H-3, H-4), 5.15
3
(m, 1H, CH), 5.37 (d, 1H, H-1, J1±2=2.7 Hz), 5.44 (m, 1H, CH), 6.18 (m, 1H, CH), 6.31
(m, 1H, CH), 7.17 (m, 2H, CH), 7.21 (m, 2H, CH), 7.52 (m, 4H, CH). 13C NMR (CDCl3),
t
t
ꢀ (ppm): 26.3 (CH3), 26.4 (CH3), 27.7 (CH2), 28.7 (CH2), 31.2 (CH3, Bu), 31.3 (CH3, Bu), 31.6
t
t
t
t
t
t
(CH3, Bu), 32.3 (CH3, Bu), 32.4 (CH3, Bu), 34.6 (C, Bu), 35.3 (C, Bu), 35.4 (C, Bu), 69.3
(d, C-5, JP±C=14.8 Hz), 70.9 (d, C-3, JP±C=6.2 Hz), 77.2 (d, C-2, JP±C=3.4 Hz), 77.4 (m, C-4),
101.8 (m, CH), 102.7 (C-1), 103.2 (m, CH), 109.9 (m, CH), 113.4 (CMe2), 124.8, 125.2, 125.4,
126.2, 127.4, 128.0, 128.5 (CH), 130.2 (C), 130.8 (CH), 131.3, 139.9, 140.5, 148.5, 148.9, 149.5
(C).
3.2.1.4. [Ir(cod)(4)]BF4 10. 82 mg (83%, white solid). Elemental analysis. Found (%): C,
47.77; H, 4.12. Calculated (%) for C40H40BF4IrO9P2: C, 47.82; H, 4.32. FAB spectrometry: m/z:
919 [M+]. 31P NMR (CDCl3), ꢀ (ppm): 104.8 (s). 31P NMR (CDCl3, 233 K), ꢀ (ppm): 103.1 (d,
2
1
2JP±P=54 Hz), 105.9 (d, JP±P=54 Hz). H NMR (CDCl3), ꢀ (ppm): 1.24 (s, 3H, CH3), 1.41 (s,
3H, CH3), 1.80±2.80 (m, 8H, CH2), 3.80±4.70 (m, 5H, H-2, H-3, H-5, H-50), 5.31 (m, 2H, CH),
5.52 (d, 1H, H-1, 3J1±2=3.9 Hz), 5.57 (m, 2H, CH), 6.80±7.80 (m, 16H, CH).
3.2.1.5. [Ir(cod)(5)]BF4 11. 109 mg (87%, red solid). Elemental analysis. Found (%): C,
.
54.58; H, 6.56. Calculated (%) for C60H80BF4IrO13P2 1/2CH2Cl2: C, 54.36; H, 6.71. FAB spec-
2
trometry: m/z: 1263 [M+]. 31P NMR (CDCl3), ꢀ (ppm): 113.6 (d, 1P, JP±P=43.1 Hz), 114.9 (d,
2
1
1P, JP±P=43.1 Hz). H NMR (CDCl3), ꢀ (ppm): 1.25 (s, 3H, CH3), 1.40 (s, 3H, CH3), 1.54 (s,
18H, CH3 tBu), 1.64 (s, 18H, CH3 tBu), 2.05 (m, 4H, CH2), 2.30 (m, 2H, CH2), 2.56 (m, 2H,
CH2), 3.22 (dd, 1H, H-2, J2±1=3.3 Hz, J2±3=3.6 Hz), 3.59 (m, 1H, H-50), 3.82 (s, 12H, OMe),
3
3
4.00 (m, 1H, H-5), 4.45 (m, 2H, H-3, H-4), 4.84 (m, 1H, CH), 5.08 (m, 1H, CH), 5.40 (d, 1H,
3
H-1, J1±2=3.3 Hz), 6.03 (m, 1H, CH), 6.14 (m, 1H, CH), 6.65 (m, 2H, CH), 6.77 (m, 2H,
CH), 7.05 (m, 4H, CH). 13C NMR (CDCl3), ꢀ (ppm): 25.9 (CH3), 26.7 (CH3), 28.4 (CH2), 29.3
(CH2), 31.0 (CH2), 31.9 (CH3, tBu), 32.3 (CH3, tBu), 32.6 (CH3, tBu), 32.9 (CH3, tBu), 35.9 (C, tBu),
36.0 (C, tBu), 56.2 (OCH3), 70.6 (d, C-5, JP±C=14.3 Hz), 71.8 (d, C-3, JP±C=6.8 Hz), 77.6 (C-2),
78.2 (d, C-4, JP±C=13.7 Hz), 92.3 (d, CH, JC±P=16.6 Hz), 93.7 (d, CH, JC±P=16.5 Hz), 101.4