T. Noël, K. Bert, E. Van der Eycken, J. Van der Eycken
5.36–5.43 (m, 1 H, CHMe), 6.59–6.64 (m, 1 H, Ph), 6.72–6.77 (m, 75 (24), 56 (52). MS (ESI): m/z = 564 [M + H]+. [α]2D0 = –367.6 (c
FULL PAPER
2 H, Ph), 6.97–7.02 (m, 2 H, Ph), 7.06–7.16 (m, 2 H, Ph), 7.27–
=
0.70, CHCl3). HRMS (EI): calcd. for C32H27NOP35ClFe
7.33 (m, 5 H, Ph), 7.45–7.51 (m, 2 H, Ph) ppm. 13C NMR 563.0868; found 563.0857.
(75.4 MHz, CDCl3): δ = 20.7 (CH3), 49.6 (d, JC,P = 8.8 Hz, CH),
(Sp)-1-[(1R)-(1-(7-Bromo-3H-isobenzofuran-1-ylideneamino)-ethyl)]-
68.7 (d, JC,P = 4.0 Hz, CH), 68.8 (CH), 69.5 (5 CH), 71.3 (d, JC,P
= 4.5 Hz, CH), 71.8 (CH2), 75.3 (d, JC,P = 6.6 Hz, 1 C), 98.3 (d,
JC,P = 23.9 Hz, 1 C), 120.5 (CH), 123.6 (CH), 126.8 (CH), 127.0
(d, JC,P = 6.3 Hz, CH), 127.4 (CH), 127.9 (d, JC,P = 7.7 Hz, CH),
128.8 (CH), 129.8 (C), 130.4 (CH), 132.0 (d, JC,P = 18.6 Hz, CH),
135.2 (d, JC,P = 20.9 Hz, CH), 137.6 (d, JC,P = 8.6 Hz, 1 C), 139.2
(d, JC,P = 9.4 Hz, 1 C), 142.8 (C), 158.0 (C) ppm. 31P NMR
2-(diphenylphosphanyl)ferrocene (5d): Yield: 74.5 mg (51%). 1H
NMR (300 MHz, CDCl3): δ = 1.64 (d, J = 6.6 Hz, 3 H, CH3), 3.61
(m, 1 H, Cp), 4.09 (s, 5 H, Cp), 4.27 (m, 1 H, Cp), 4.65–4.70 (m,
2 H, 1 H from CH2O + 1 H from Cp), 4.99 (d, J = 14.3 Hz, 1 H,
CH2O), 5.31–5.39 (m, 1 H, CHMe), 6.53–6.58 (m, 1 H, Ph), 6.75–
6.81 (m, 2 H, Ph), 6.97–7.02 (m, 3 H, Ph), 7.08–7.13 (m, 1 H, Ph),
7.31–7.51 (m, 6 H, Ph) ppm. 13C NMR (75.4 MHz, CDCl3): δ =
21.3 (CH3), 49.8 (d, JC,P = 8.7 Hz, CH), 68.8 (d, JC,P = 4.0 Hz,
CH), 68.9 (CH), 69.5 (5 CH), 70.1 (CH2), 71.0 (d, JC,P = 4.4 Hz,
CH), 75.0 (d, JC,P = 6.1 Hz, 1 C), 99.1 (d, JC,P = 23.9 Hz, 1 C),
119.2 (C), 119.6 (CH), 126.5 (CH), 127.1 (d, JC,P = 6.2 Hz, CH),
127.9 (d, JC,P = 7.7 Hz, CH), 128.2 (C), 128.9 (CH), 130.9 (CH),
131.9 (d, JC,P = 18.3 Hz, CH), 132.9 (CH), 135.3 (d, JC,P = 21.0 Hz,
CH), 137.8 (d, JC,P = 8.9 Hz, 1 C), 139.2 (d, JC,P = 10.0 Hz, 1
C), 145.7 (C), 154.4 (C) ppm. 31P NMR (121.4 MHz, CDCl3): δ =
(121.4 MHz, CDCl ): δ = –22.5 ppm. IR (HATR): ν = 3050, 2972,
˜
3
2931, 2873, 1681, 1469, 1451, 1433, 1363, 1290, 1243, 1167, 1106,
1081, 1044, 1017, 1000, 819, 747, 728, 697 cm–1. MS (EI): m/z (%)
= 529 (8) [M]+, 396 (19), 275 (8), 212 (9), 183 (17), 165 (15), 133
(11), 121 (100), 77 (17), 56 (30). MS (ESI): m/z = 530 [M + H]+.
[α]2D0
= –338.8 (c = 0.64, CHCl3). HRMS (EI): calcd. for
C32H28NOPFe 529.1258; found 529.1257.
(Sp)-1-[(1R)-(1-(5-Chloro-3H-isobenzofuran-1-ylideneamino)-ethyl)]-
2-(diphenylphosphanyl)ferrocene (5b): Yield: 134.0 mg (99%). 1H
NMR (300 MHz, CDCl3): δ = 1.63 (d, J = 6.6 Hz, 3 H, CH3), 3.66
(m, 1 H, Cp), 4.11 (s, 5 H, Cp), 4.30 (s, 1 H, Cp), 4.67 (m, 1 H,
Cp), 4.83 (d, J = 14.4 Hz, 1 H, CH2O), 5.09 (d, J = 14.4 Hz, 1 H,
CH2O), 5.37–5.44 (m, 1 H, CHMe), 6.70–6.75 (m, 1 H, Ph), 6.80–
6.84 (m, 2 H, Ph), 6.99–7.04 (m, 2 H, Ph), 7.09–7.28 (m, 3 H, Ph),
7.34–7.35 (m, 3 H, Ph), 7.47–7.53 (m, 2 H, Ph) ppm. 13C NMR
(75.4 MHz, CDCl3): δ = 20.5 (CH3), 49.8 (d, JC,P = 8.8 Hz, CH),
68.7 (d, JC,P = 4.0 Hz, CH), 68.9 (CH), 69.5 (5 CH), 71.1 (CH2),
71.4 (d, JC,P = 4.4 Hz, CH), 75.3 (d, JC,P = 6.6 Hz, 1 C), 98.2 (d,
JC,P = 23.7 Hz, 1 C), 120.9 (CH), 124.7 (CH), 126.9 (CH), 127.1
(d, JC,P = 6.2 Hz, CH), 127.9 (d, JC,P = 7.7 Hz, CH), 128.03 (CH),
128.7 (C), 128.8 (CH), 132.0 (d, JC,P = 18.6 Hz, CH), 135.2 (d, JC,P
= 20.9 Hz, CH), 136.5 (C), 137.5 (d, JC,P = 8.7 Hz, 1 C), 139.3 (d,
JC,P = 9.8 Hz, 1 C), 144.4 (C), 156.5 (C) ppm. 31P NMR
–22.0 ppm. IR (HATR): ν = 3052, 2971, 2930, 1680, 1580, 1478,
˜
1458, 1433, 1361, 1321, 1303, 1266, 1244, 1217, 1106, 1079, 1039,
1000, 892, 819, 774, 741, 696, 668 cm–1. MS (EI): m/z (%) = 607
(5) [M]+, 396 (100), 331 (22), 319 (10), 288 (22), 252 (18), 211 (20),
182 (34), 165 (27), 121 (57), 102 (27), 56 (55). MS (ESI): m/z =
607.9 [M + H]+. [α]2D0 = –322.2 (c = 0.99, CHCl3). HRMS (EI):
calcd. for C32H27NOP79BrFe 607.0363; found 607.0382.
Synthesis of Imine–Phosphane Ligand 6:
A suspension of
(Sp)-1-[(1R)-(1-aminoethyl)]-2-(diphenylphosphanyl)ferrocene (3;
100.0 mg, 0.24 mmol), MgSO4 (200 mg), and benzaldehyde
(24.6 µL, 0.24 mmol) in CH2Cl2 (2 mL) was stirred for 24 h. Evapo-
ration in vacuo and purification by flash chromatography over ba-
sic alumina (Et2O) resulted in the corresponding ligand 6 as a yel-
1
low oil. Yield: 108.3 mg (90%). H NMR (300 MHz, CDCl3): δ =
1.69 (d, J = 6.7 Hz, 3 H, CH3), 3.77 (m, 1 H, Cp), 4.09 (s, 5 H,
Cp), 4.35 (m, 1 H, Cp), 4.70 (m, 1 H, Cp), 4.83 (m, 1 H, CHMe),
6.76–6.81 (m, 1 H, Ph), 6.85–6.90 (m, 2 H, Ph), 6.97–7.02 (m, 2 H,
Ph), 7.11–7.24 (m, 5 H, Ph), 7.36–7.38 (m, 3 H, Ph), 7.50–7.56 (m,
2 H, Ph), 8.03 (s, 1 H, CNH) ppm. 13C NMR (75.4 MHz, CDCl3):
δ = 21.9 (CH3), 64.3 (d, JC,P = 6.8 Hz, CH), 69.3 (CH), 69.3 (d,
JC,P = 4.1 Hz, CH), 69.6 (5 CH), 71.6 (d, JC,P = 4.6 Hz, CH), 75.5
(d, JC,P = 7.7 Hz, 1 C), 96.6 (d, JC,P = 23.3 Hz, 1 C), 127.3 (CH),
127.6 (CH), 127.7 (2 CH), 127.7 (CH), 128.0 (CH), 128.0 (2 CH),
128.1 (CH), 129.0 (CH), 129.8 (CH), 132.3 (CH), 132.6 (CH), 135.1
(CH), 135.4 (CH), 135.9 (C), 137.5 (d, JC,P = 8.5 Hz, 1 C), 138.6
(d, JC,P = 8.5 Hz, 1 C), 160.1 (CH) ppm. 31P NMR (121.4 MHz,
(121.4 MHz, CDCl ): δ = –22.6 ppm. IR (HATR): ν = 3067, 2969,
˜
3
2931, 2871, 2358, 2341, 1689, 1613, 1473, 1456, 1432, 1354, 1304,
1265, 1242, 1222, 1192, 1167, 1106, 1080, 1042, 1018, 879, 822,
742, 697, 668 cm–1. MS (EI) m/z (%) = 563 (5) [M]+, 396 (100), 331
(20), 288 (20), 252 (15), 226 (6), 183 (18), 167 (39), 138 (68), 102
(27), 75 (24), 56 (45). MS (ESI): m/z = 564 [M + H]+. [α]2D0 = –338.1
(c = 0.64, CHCl3). HRMS (EI): calcd. for C32H27NOP35ClFe
563.0868; found 563.0888.
(Sp)-1-[(1R)-(1-(7-Chloro-3H-isobenzofuran-1-ylideneamino)-ethyl)]-
2-(diphenylphosphanyl)ferrocene (5c): Yield: 82.5 mg (61%). 1H
NMR (300 MHz, CDCl3): δ = 1.64 (d, J = 6.6 Hz, 3 H, CH3), 3.62
(m, 1 H, Cp), 4.08 (s, 5 H, Cp), 4.27 (m, 1 H, Cp), 4.65 (m, 1 H,
Cp), 4.72 (d, J = 14.3 Hz, 1 H, CH2O), 5.01 (d, J = 14.3 Hz, 1 H,
CH2O), 5.33–5.41 (m, 1 H, CHMe), 6.54–6.59 (m, 1 H, Ph), 6.75–
6.80 (m, 2 H, Ph), 6.93–7.02 (m, 3 H, Ph), 7.14–7.21 (m, 2 H, Ph),
7.30–7.35 (m, 3 H, Ph), 7.45–7.52 (m, 2 H, Ph) ppm. 13C NMR
(75.4 MHz, CDCl3): δ = 21.1 (CH3), 50.0 (d, JC,P = 8.8 Hz, CH),
68.8 (d, JC,P = 3.9 Hz, CH), 68.9 (CH), 69.5 (5 CH), 70.4 (CH2),
CDCl ): δ = –23.8 ppm. IR (HATR): ν = 3052, 2966, 2932, 2848,
˜
3
1638, 1477, 1449, 1433, 1373, 1364, 1299, 1262, 1240, 1218, 1167,
1106, 1080, 1069, 1039, 1026, 1000, 967, 908, 818, 739, 691 cm–1.
MS (ESI): m/z = 502.1 [M + H]+. [α]2D0 = –440.0 (c = 0.93, CHCl3).
HRMS (EI): calcd. for C31H28NPFe 501.1309; found 501.1319.
Synthesis of Amidine–Phosphane Ligand 7:[16]
A mixture of
71.0 (d, JC,P = 4.3 Hz, CH), 75.1 (d, JC,P = 6.1 Hz, 1 C), 99.0 (d, (Sp)-1-[(1R)-(1-aminoethyl)]-2-(diphenylphosphanyl)ferrocene (3;
JC,P = 24.2 Hz, 1 C), 118.9 (CH), 126.6 (CH), 126.7 (C), 127.0 (d, 100.0 mg, 0.24 mmol) and N,N-dimethylformamide dimethylacetal
JC,P = 6.1 Hz, CH), 127.9 (d, JC,P = 7.7 Hz, CH), 128.8 (CH), 129.5 (2 mL, 15.0 mmol) was stirred at room temperature for 4 h. The
(CH), 130.8 (CH), 131.2 (C), 131.9 (d, JC,P = 18.3 Hz, CH), 135.3 volatiles were removed in vacuo, resulting in 7 as a brownish oil.
(d, JC,P = 21.0 Hz, CH), 137.7 (d, JC,P = 8.8 Hz, 1 C), 139.2 (d,
Yield: 112.4 mg (100%). 1H NMR (300 MHz, CDCl3): δ = 1.53 (d,
J = 6.6 Hz, 3 H, CH3), 2.20 [s, 6 H, N(CH3)2] 3.69 (m, 1 H, Cp),
3.96 (s, 5 H, Cp), 4.24 (m, 1 H, Cp), 4.54 (m, 1 H, CHMe), 4.59
(m, 1 H, Cp), 7.06–7.15 (m, 6 H, Ph + 1 H from CNH), 7.32–7.34
(m, 3 H, Ph), 7.47–7.52 (m, 2 H, Ph) ppm. 13C NMR (75.4 MHz,
JC,P = 9.9 Hz, 1 C), 145.6 (C), 154.5 (C) ppm. 31P NMR
(121.4 MHz, CDCl ): δ = –22.0 ppm. IR (HATR): ν = 3054, 2972,
˜
3
2931, 1678, 1606, 1585, 1478, 1462, 1433, 1361, 1306, 1265, 1244,
1220, 1167, 1106, 1078, 1040, 1026, 1000, 915, 818, 774, 738, 698,
668 cm–1. MS (EI): m/z (%) = 563 (7) [M]+, 396 (100), 331 (21), CDCl3): δ = 22.8 (CH3), 37.5 (2 CH3), 59.4 (d, JC,P = 6.2 Hz, CH),
288 (21), 252 (17), 226 (6), 183 (20), 167 (32), 138 (60), 102 (31),
68.9 (CH), 69.2 (d, JC,P = 4.5 Hz, CH), 69.4 (5 CH), 71.3 (d, JC,P
4060
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Eur. J. Org. Chem. 2010, 4056–4061