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Organic & Biomolecular Chemistry
6.77–6.66 (m, 3H, [M + m]), 6.63 (d, 2H, [m], J = 9.0 Hz), 124.7, 123.9, 122.1, 122.1, 121.6, 118.9, 115.5, 115.4, 114.8,
6.58–6.51 (m, 1H, [m]), 6.50–6.45 (m, 1H, [M]), 4.82 (t, 1H, [M], 113.2, 112.4, 96.1 (d, J(C, Rh) = 6.2 Hz), 95.9 (d, J(C, Rh) =
J = 8.3 Hz), 4.70 (d, 1H, [m], J = 5.2 Hz), 4.66 (d, 1H, [M], J = 6.3 Hz), 87.7, 87.3, 64.4, 63.5, 55.4, 55.4, 9.1, 8.9. IR (CH2Cl2):
5.2 Hz), 4.60 (d, 1H, [m], J = 5.2 Hz), 4.42–4.26 (m, 1H, [m]),
4.34 (d, 1H, [M], J = 5.2 Hz), 4.20–4.04 (m, 2H, [M + m]), C37H36N2O3Rh: 659.1775, found 659.1744.
3.56–3.42 (m, 1H, [m]), 3.43 (t, 1H, [M], J = 8.3 Hz), 3.31 (s, 3H, Iridium complex cis-20a. Following the general procedure,
ν = . HRMS ESI: m/z: [M −
1759 cm−1 Cl]+ calcd for
[M]), 3.27 (s, 3H, [m]), 1.47 (s, 15H, [M]), 1.46 (s, 15H, [m]). from β-lactam cis-18 (18.5 mg, 38 μmol), [IrCp*Cl2]2 (15.0 mg,
13C NMR (75 MHz, benzene-d6, 50 °C): δ = 178.8 (d, J(C, Rh) = 19 μmol) and NaOAc (7.4 mg, 90 μmol) in 2.0 mL of CH2Cl2
32.3 Hz), 165.3, 165.3, 165.2, 165.2, 160.6, 160.2, 158.0, 157.1, and after precipitation, a 4 : 1 diastereomeric mixture of cis-
156.8, 156.7, 151.7, 151.4, 144.8, 138.7, 138.3, 137.5, 137.3, 20a (29.2 mg, 34 μmol, 90%) was obtained as a yellow solid. 1H
136.7, 136.4, 135.7, 135.0, 132.9, 132.3, 129.4, 128.7, 128.6, NMR (300 MHz, CDCl3): δ = 8.65 (d, 1H, [m], J = 5.6 Hz), 8.59
124.1, 123.8, 123.3, 122.8, 122.2, 121.9, 119.6, 119.2, 119.0, (d, 1H, [M], J = 5.8 Hz), 8.24 (d, 1H, [m], J = 2.1 Hz), 7.72
114.9, 114.8, 96.2 (d, J(C, Rh) = 6.1 Hz), 96.0 (d, J(C, Rh) = (d, 1H, [M], J = 8.0 Hz), 7.69–7.58 (m, 6H, [M + m]), 7.46–7.32
6.1 Hz), 70.6, 70.4, 64.8, 63.8, 62.1, 61.9, 59.8, 55.2, 9.2, 9.1. (m, 10H, [M + m]), 7.28–7.20 (m, 4H, [M + m]), 7.17 (bs, 1H,
IR (CHCl3): ν = 1753 cm−1. HRMS ESI: m/z: [M − Cl]+ calcd for [M]), 7.02 (t, 2H, [M + m], J = 6.5 Hz), 6.93–6.82 (m, 4H,
C40H39N3O4Rh: 728.1990, found 728.2022.
[M + m]), 6.55 (dd, 1H, [m], J = 8.3, 2.1 Hz), 5.28 (d, 1H, [M],
Rhodium complex cis-19b. Following the general procedure, J = 5.1 Hz), 5.16 (d, 1H, [m], J = 5.2 Hz), 4.67 (d, 1H, [m], J =
from β-lactam cis-17 (14.4 mg, 34 μmol), [RhCp*Cl2]2 (10.5 mg, 5.2 Hz), 4.65–4.56 (m, 1H, [m]), 4.60 (d, 1H, [M], J = 5.2 Hz),
17 μmol) and NaOAc (6.6 mg, 80 μmol) in 2.0 mL of CH2Cl2 4.50 (dd, 1H, [M], J = 8.8, 6.9 Hz), 4.35–4.25 (m, 2H, [M + m]),
and after precipitation, a 3.2 : 1 diastereomeric mixture of cis- 4.00 (dd, 2H, [M + m], J = 8.8, 6.9 Hz), 3.83 (s, 3H, [m]), 3.82
19b (21.7 mg, 31 μmol, 92%) was obtained as an orange solid. (s, 3H, [M]), 1.67 (s, 15H, [m]), 1.42 (s, 15H, [M]). 13C NMR
1H NMR (300 MHz, benzene-d6, 50 °C): δ = 9.05 (d, 1H, [m], J = (75 MHz, CDCl3): δ = 166.9, 166.8, 165.0, 164.5, 161.2, 161.1,
1.8 Hz), 8.65 (d, 1H, [m], J = 5.6 Hz), 8.59 (d, 1H, [M], J = 160.2, 159.9, 157.6, 157.4, 151.5, 141.1, 141.0, 139.6, 139.1,
5.5 Hz), 8.30 (dd, 1H, [M], J = 8.3, 1.9 Hz), 7.58 (d, 1H, [M], 137.5, 137.4, 137.4, 137.2, 129.9, 129.7, 129.5, 129.3, 127.9,
J = 8.4 Hz), 7.50–7.37 (m, 5H, [M + m]), 7.36–7.28 (m, 1H, [M]), 127.8, 125.5, 125.3, 125.1, 125.0, 124.6, 124.5, 123.0, 122.2,
7.19–7.01 (m, 7H, [M + m]), 6.98 (d, 3H, [M + m], J = 8.0 Hz), 119.1, 114.6, 114.5, 113.3, 111.4, 89.2, 88.8, 86.7, 70.9,
6.84 (t, 3H, [M + m], J = 7.2 Hz), 6.78–6.70 (m, 4H, [M + m]), 70.8, 63.2, 63.0, 61.9, 61.4, 60.1, 59.9, 55.7, 55.6, 9.2, 9.0.
6.69–6.56 (m, 4H, [M + m]), 5.38 (d, 1H, [m], J = 4.9 Hz), 5.34 IR (CHCl3): ν = 1758 cm−1. HRMS ESI: m/z: [M − Cl]+ calcd for
(d, 1H, [M], J = 4.9 Hz), 5.20 (d, 1H, [m], J = 4.9 Hz), 4.94 C40H39IrN3O4: 818.2567, found 818.2594.
(d, 1H, [M], J = 4.9 Hz), 3.33 (s, 3H, [M]), 3.29 (s, 3H, [m]), 1.36
Iridium complex trans-20a. Following the general proce-
(s, 30H, [M + m]). 13C NMR (75 MHz, benzene-d6, 50 °C): δ = dure, from β-lactam trans-18 (8.1 mg, 16 μmol), [IrCp*Cl2]2
181.2 (d, J(C, Rh) = 32.6 Hz), 165.5, 165.5, 164.1, 163.7, 160.7, (6.6 mg, 8 μmol) and NaOAc (3.2 mg, 39 μmol) in 1.0 mL of
160.6, 158.4, 158.2, 151.8, 151.7, 141.0, 139.4, 138.9, 138.9, CH2Cl2 and after precipitation, a 3.2 : 1 diastereomeric mixture
137.2, 130.6, 130.3, 129.8, 129.8, 129.2, 126.9, 126.7, 125.2, of trans-20a (13.2 mg, 15 μmol, 94%) was obtained as a yellow
124.9, 124.3, 122.3, 121.6, 121.4, 119.3, 116.7, 116.5, 114.5, solid. 1H NMR (300 MHz, CDCl3): δ = 8.67–8.60 (m, 2H,
114.5, 96.5 (d, J(C, Rh) = 6.2 Hz), 96.2 (d, J(C, Rh) = 6.2 Hz), [M + m]), 7.93 (s, 1H, [m]), 7.73 (d, 1H, [M], J = 8.1 Hz),
82.2, 82.1, 61.9, 55.1, 55.0, 9.5, 9.2. IR (CHCl3): ν = 1754 cm−1
HRMS ESI: m/z: [M − Cl]+ calcd for C37H36N2O3Rh: 659.1775, 7.49–7.26 (m, 12H, [M + m]), 7.09–7.00 (m, 6H, [M + m]),
found 659.1811. 6.87–6.80 (m, 5H, [M + m]), 6.40 (dd, 1H, [m], J = 8.3, 2.1 Hz),
.
7.67–7.62 (m, 2H, [M + m]), 7.60 (d, 2H, [M + m], J = 8.3 Hz),
Rhodium complex trans-19b. Following the general pro- 5.12 (dd, 1H, [m], J = 9.0, 6.3 Hz), 5.07 (dd, 1H, [M], J = 9.0,
cedure, from β-lactam trans-17 (14.3 mg, 34 μmol), 6.1 Hz), 4.97 (d, 1H, [m], J = 2.4 Hz), 4.93 (d, 1H, [M], J =
[RhCp*Cl2]2 (10.4 mg, 17 μmol) and NaOAc (6.6 mg, 80 μmol) 2.4 Hz), 4.77 (t, 2H, [M + m], J = 9.0 Hz), 4.44 (dd, 1H, [M], J =
in 2.0 mL of CH2Cl2 and after precipitation, a 4.7 : 1 diastereo- 9.0, 6.1 Hz), 4.38 (dd, 1H, [m], J = 9.0, 6.3 Hz), 4.06 (d, 1H, [m],
meric mixture of trans-19b (22.2 mg, 32 μmol, 94%) was J = 2.4 Hz), 3.96 (d, 1H, [M], J = 2.4 Hz), 3.77 (s, 3H, [m]), 3.75
obtained as an orange solid. 1H NMR (300 MHz, CDCl3): δ = (s, 3H, [M]), 1.64 (s, 15H, [m]), 1.42 (s, 15H, [M]). 13C NMR
8.58 (d, 2H, [M + m], J = 5.6 Hz), 7.87 (d, 1H, [m], J = 2.1 Hz), (75 MHz, CDCl3): δ = 166.4, 164.4, 164.2, 162.4, 162.3, 160.0,
7.62–7.55 (m, 4H, [M + m]), 7.51 (d, 1H, [M], J = 2.0 Hz), 7.45 159.9, 157.3, 157.1, 151.1, 140.8, 138.5, 138.0, 137.8, 137.3,
(d, 1H, [M], J = 8.4 Hz), 7.40–7.32 (m, 5H, [M + m]), 7.26–7.14 136.9, 136.9, 130.4, 129.9, 129.6, 129.5, 128.3, 127.6, 127.5,
(m, 4H, [M + m]), 7.04–6.98 (m, 2H, [M + m]), 6.97–6.86 127.3, 127.1, 124.5, 124.4, 124.0, 123.7, 121.9, 118.8, 118.7,
(m, 7H, [M + m]), 6.86–6.80 (m, 5H, [M + m]), 5.05 (d, 1H, [M], 114.6, 112.8, 111.0, 88.7, 88.5, 70.2, 69.9, 69.1, 68.6, 61.1, 60.0,
J = 1.7 Hz), 5.03 (d, 1H, [m], J = 1.7 Hz), 5.01 (d, 1H, [M], J = 58.7, 58.6, 55.4, 55.3, 8.8, 8.5. IR (CH2Cl2): ν = 1755 cm−1
.
1.7 Hz), 4.93 (d, 1H, [m], J = 1.7 Hz), 3.77 (s, 3H, [m]), 3.75 HRMS ESI: m/z: [M − Cl]+ calcd for C40H39IrN3O4: 818.2567,
(s, 3H, [M]), 1.53 (s, 15H, [m]), 1.38 (s, 15H, [M]). 13C NMR found 818.2558.
(75 MHz, CDCl3, [M]): δ = 179.8 (d, J(C, Rh) = 32.8 Hz), 164.5,
Iridium complex 35a. Following the general procedure,
162.9, 162.8, 160.2, 160.2, 157.1, 151.1, 151.0, 140.4, 140.3, from β-lactam 34 (20.0 mg, 42 μmol), [IrCp*Cl2]2 (33.9 mg,
137.5, 137.0, 136.9, 129.6, 128.2, 128.1, 128.0, 127.7, 125.4, 42 μmol) and NaOAc (16.3 mg, 199 μmol) in 2.0 mL of CH2Cl2
294 | Org. Biomol. Chem., 2014, 12, 286–297
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