Rh-Catalyzed Hydrogenation with Chiral Aminophosphanes
(Saze,Rbin)-4d: This compound was prepared as above from Saze-1a
(0.560 g, 1.90 mmol), (R)-1,1Ј-binaphthyl-2,2Ј-diyl chlorophosphite
of [PtCl2(PhCN)2] (0.072 g, 0.153 mmol) in CH2Cl2 (10 mL). After
stirring for 24 h, the solution was concentrated to 6 mL, whereupon
(0.680 g, 1.90 mmol) and diisopropylethylamine (0.245 g, n-pentane (30 mL) was added. Cooling the solution to –10 °C
1.90 mmol, ca. 0.33 mL); yield 0.878 g, 76 %. C42H28NO2P
(609.65): calcd. C 82.7, H 4.6, N 2.3; found C 82.8, H 4.6, N 2.3.
NMR as for (Raze,Sbin)-4c. [α]2D0 = 62.4 (c = 0.28, CHCl3). MS (ESI-
TOF): m/z = 610.2 (100%, [M + H]+; C42H29NO2P requires 610.2).
caused complex 7 to precipitate as a white solid, which was col-
lected by filtration; yield 0.190 g, 97 %. C68H48Cl2N2O4P2Pt
(1285.05): calcd. C 63.6, H 3.8, N 2.2; found C 63.4, H 3.7, N 2.0.
1H NMR (300 MHz, CDCl3): δ = 7.93 (d, JH,H = 8.2 Hz, 4 H,
arom. H), 7.80 (d, JH,H = 8.1 Hz, 4 H, arom. H), 7.58 (d, JH,H
=
(Saze)-5a: This compound was prepared as above from Saze-1a
(0.119 g, 0.40 mmol), 1,1Ј-binaphthyl-2,2Ј-diyl chlorophosphite
(0.101 g, 0.40 mmol) and diisopropylethylamine (0.052 g,
0.40 mmol, ca. 0.07 mL); yield 0.160 g, 78 %. C34H24NO2P
(509.53): calcd. C 80.1, H 4.8, N 2.8; found C 80.3, H 4.8, N 2.8.
1H NMR (300 MHz, CDCl3): δ = 7.98 (t, JH,H = 7.7 Hz, 4 H,
arom. H), 7.53–7.05 (m, 15 H, arom. H), 6.81 (d, JH,H = 7.9 Hz, 1
7.9 Hz, 2 H, arom. H), 7.49 (t, JH,H = 7.3 Hz, 4 H, arom. H), 7.59–
7.12 (m, 18 H, arom. H), 7.15 (t, JH,H = 7.1 Hz, 4 H, arom. H),
6.83 (t, JH,H = 7.2 Hz, 2 H, arom. H), 6.56 (d, JH,H = 5.5 Hz, 2 H,
2
arom. H), 4.68 (br. s, 4 H, ArCH2), 3.19 (d, JH,H = 11.7 Hz, 4 H,
ArCH2) ppm. 13C NMR (75 MHz, CDCl3): δ = 149.77 (br. s, quat.
C), 148.92 (br. s, quat. C), 135.29 (s, quat. C), 133.38 (s, quat. C),
131.76 (s, quat. C), 131.21 (s, quat. C), 130.47 (s, arom. CH), 130.16
(s, arom. CH), 129.60 (s, arom. CH), 129.55 (s, quat. C), 129.15 (s,
arom. CH), 129.06 (s, quat. C), 128.41 (s, arom. CH), 127.47 (s,
arom. CH), 126.42 (s, arom. CH), 126.04 (s, arom. CH), 123.51 (s,
arom. CH), 121.21 (s, arom. CH), 48.99 (s, ArCH2) ppm. 31P NMR
(121 MHz, CDCl3): δ = 85.3 (1JPt,P = 5580 Hz) ppm. M.p. Ͼ
250 °C. MS (ESI-TOF): m/z = 1323.74 (93 %, [M + K]+;
C68H48Cl2KN2O4P2Pt requires 1323.18).
H, arom. H), 4.40 and 3.57 (ABX spectrum, JAX = 7.5 Hz, JBX
=
6.9 Hz, JAB = 12.8 Hz, 4 H, ArCH2) ppm. 13C NMR (75 MHz,
CDCl3): δ = 152.04 (d, JC,P = 5.6 Hz, 1 C, quat. C), 151.22 (d, JC,P
= 4.4 Hz, quat. C), 135.30 (s, quat. C), 133.52 (d, JC,P = 3.7 Hz,
quat. C), 133.30 (s, quat. C), 131.48 (s, quat. C), 131.45 (s, quat.
C), 131.07 (d, JC,P = 2.5 Hz, quat. C), 129.99 (s, arom. CH), 129.73
(s, arom. CH), 129.36 (s, arom. CH), 129.24 (s, arom. CH), 128.42
(s, arom. CH), 127.53 (s, arom. CH), 127.41 (s, arom. CH), 126.03
(s, arom. CH), 125.76 (s, arom. CH), 124.90 (s, arom. CH), 124.55
(s, arom. CH), 122.53 (s, arom. CH), 121.91 (s, arom. CH), 47.83
trans-Dichloroplatinum(II) Complex 8: A solution of (Raze,Rbin)-3b
(0.121 g, 0.174 mmol) in CH2Cl2 (8 mL) was added to a solution
of PtCl2(PhCN)2 (0.041 g, 0.087 mmol) in CH2Cl2 (10 mL). After
stirring for 24 h, the solution was concentrated to 6 mL, upon
which n-pentane (30 mL) was added. Cooling the solution to
–10 °C caused complex 8 to precipitate as a white solid, which was
filtered; yield 0.134 g, 93%. C100H74Cl2N4P2Pt (1659.62): calcd. C
2
(d, JC,P = 21.1 Hz, ArCH2) ppm. 31P NMR (121 MHz, CDCl3): δ
= 144.9 (s) ppm. [α]2D0 = 120.0 (c = 1.60, CH2Cl2). MS (EI): m/z =
509.1 (37%, [M]+; C34H24NO2P requires 509.2).
(Raze)-5b: This compound was obtained as above using Raze-1b
(0.080 g, 0.27 mmol), 1,1Ј-binaphthyl-2,2Ј-diyl chlorophosphite
(0.068 g, 0.27 mmol) and diisopropylethylamine (0.035 g, 72.4, H 4.5, N 3.4; found C 72.4, H 4.4, N 3.4. 1H NMR (300 MHz,
0.27 mmol, ca. 0.05 mL); yield 0.090 g, 65 %. C34H24NO2P
(509.53): calcd. C 80.1, H 4.8, N 2.8; found C 80.0, H 4.8, N 2.7.
NMR as for (Saze)-5a. M.p. 144–146 °C; [α]2D0 = –118.8 (c = 1.60,
CH2Cl2). MS (EI): m/z = 509.1 (38%, [M]+; C34H24NO2P requires
509.2).
CDCl3): δ = 7.95–7.90 (m, 8 H, arom. H), 7.82–7.69 (m, 13 H,
arom. H), 7.57–7.37 (m, 29 H, arom. H), 7.28–7.21 (m, 8 H, arom.
3
H), 4.99 (virtual t, JH,P
(virtual t, JH,P
+
5JH,PЈ = 6.3 Hz, 2 H, ArCH2), 4.95
+
5JH,PЈ = 7.3 Hz, 2 H, ArCH2), 4.72 (virtual t,
3
3JH,P + 5JH,PЈ = 7.4 Hz, 2 H, ArCH2), 4.67 (virtual t, 3JH,P + 5JH,PЈ
= 7.4 Hz, 2 H, ArCH2), 3.89–3.83 (m, 8 H, ArCH2) ppm. 13C
NMR (75 MHz, CDCl3): δ = 135.26 (s, quat. C), 133.80 (s, arom.
CH), 133.54 (d, JC,P = 5.6 Hz, quat. C), 133.50 (d, JC,P = 5.6 Hz,
quat. C), 133.19 (s, quat. C), 133.18 (d, JC,P = 5.0 Hz, arom. CH),
131.41 (s, quat. C), 131.27 (s, quat. C), 130.36 (s, arom. CH), 129.53
(s, arom. CH), 128.89 (s, arom. CH), 128.62 (s, arom. CH), 128.36
(s, arom. CH), 128.28 (s, arom. CH), 127.67 (s, arom. CH), 127.59
(s, arom. CH), 125.79 (s, arom. CH), 125.71 (s, arom. CH), 125.61
(s, arom. CH), 125.54 (s, arom. CH), 50.82 (virtual t, 2JC,P + 4JC,PЈ
= 6.8 Hz, ArCH2), 50.64 (virtual t, 2JC,P + 4JC,PЈ = 6.8 Hz, ArCH2)
ppm. 31P NMR (121 MHz, CDCl3): δ = 81.4 (1JPt,P = 2945 Hz)
ppm. M.p. Ͼ 250 °C. MS (MALDI-TOF): m/z = 1622.54 (5 %,
[M – Cl]+; C100H74ClN4P2Pt requires 1622.48).
trans-Dichloroplatinum(II) Complex 6: A solution of Saze-2a
(0.133 g, 0.277 mmol) in CH2Cl2 (8 mL) was added to a solution
of [PtCl2(PhCN)2] (0.066 g, 0.139 mmol) in CH2Cl2 (10 mL). After
stirring for 24 h, the solution was concentrated to 6 mL, whereupon
n-pentane (30 mL) was added. Cooling the solution to –10 °C
caused complex 5 to precipitate as a white solid, which was filtered;
yield 0.161 g, 95%. C68H52Cl2N2P2Pt (1225.09): calcd. C 66.7, H
4.3, N 2.3; found C 66.7, H 4.4, N 2.2. 1H NMR (300 MHz,
CDCl3): δ = 7.91 (d, JH,H = 8.1 Hz, 4 H, arom. H), 7.84 (d, JH,H
= 8.3 Hz, 4 H, arom. H), 7.73–7.66 (m, 4 H, arom. H), 7.59–7.51
(m, 4 H, arom. H), 7.47–7.38 (m, 14 H, arom. H), 7.32–7.16 (m,
3
14 H, arom. H), 4.77 (virtual t, JH,P
+
5JH,PЈ = 7.8 Hz, 2 H,
ArCH2), 4.73 (virtual t, 3JH,P + 5JH,PЈ = 7.8 Hz, 2 H, ArCH2), 3.75
3
(virtual t, JH,P
+
5JH,PЈ = 5.5 Hz, 2 H, ArCH2), 3.70 (virtual t,
Crystal Data for 6: Crystals of 6 suitable for X-ray diffraction were
obtained by slow diffusion of n-heptane into a toluene solution of
the complex. PtCl2P2C75H60N2, M = 1317.18, triclinic, space group
P1, a = 10.5246(7), b = 13.1551(6), c = 14.2077(9) Å, V =
1799.25(2) Å3, Z = 1, Dx = 1.216 gcm–3, λ(Mo-Kα) = 0.71073 Å, µ
= 2.107 cm– 1 , F(000) = 666, T = 293(2) K. The sample
(0.32ϫ0.32ϫ0.22 mm) was studied with an Oxford Diffraction
Xcalibur Saphir 3 diffractometer with graphite-monochromatized
Mo-Kα radiation. The data collection was carried out using Crys-
Alis RED.[39] 17184 Reflections were collected (2.76ϽθϽ32.09°),
12472 observations with IϾ2.0σ(I). The structure was solved with
SIR-97[40], which revealed the non-hydrogen atoms of the molecule.
After anisotropic refinement, many hydrogen atoms could be local-
ized with a Fourier difference. The whole structure was refined with
SHELXL-97[41] Hydrogen atoms were included and refined using
3JH,P + 5JH,PЈ = 5.2 Hz, 2 H, ArCH2). 13C NMR (75 MHz, CDCl3):
1
δ = 135.15 (s, quat. C), 133.63 (virtual t, JC,P
+
3JC,PЈ = 5.0 Hz,
quat. C), 133.29 (s, quat. C), 133.15 (d, JC,P = 13.0 Hz, arom. CH),
133.07 (d, JC,P = 13.0 Hz, arom. CH), 131.35 (s, quat. C), 130.44
(s, arom. CH), 130.18 (s, arom. CH), 129.11 (s, arom. CH), 128.40
(s, arom. CH), 127.99 (s, arom. CH), 127.91 (s, arom. CH), 127.82
(s, arom. CH), 127.79 (s, arom. CH), 127.78 (s, quat. C), 127.64 (s,
arom. CH), 125.87 (s, arom. CH), 125.73 (s, arom. CH), 52.30 (vir-
2
4
tual t, JC,P + JC,PЈ = 6.8 Hz, ArCH2) ppm. 31P NMR (121 MHz,
CDCl3): δ = 81.4 (1JPt,P = 2743 Hz) ppm. M.p. Ͼ 250 °C. MS (ESI-
TOF): m/z = 1230.32 (82 %, [M + Li]+; C68H52Cl2N2P2PtLi re-
quires 1230.28).
cis-Dichloroplatinum(II) Complex 7: A solution of (Raze)-5a
(0.156 g, 0.306 mmol) in CH2Cl2 (8 mL) was added to a solution
Eur. J. Org. Chem. 2007, 5395–5403
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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