Novel P,N Ligands for Asymmetric Catalysis
FULL PAPER
128.94 (d, J ϭ 1.7 Hz, arom. C), 128.78 (s, arom. C), 128.59 (d, olef. C), 105.38 (dd, J ϭ 7.9, 7.9 Hz, olef. C), 124.88 (d, J ϭ
J ϭ 0.4 Hz, arom. C), 127.55 (s, arom. C), 127.22 (s, arom. C), 23.1 Hz, arom. C), 129.79 (d, J ϭ 5.1 Hz, arom. C), 132.01 (d, J ϭ
126.80 (s, arom. C), 126.31 (s arom. C), 126.26 (s, arom. C), 125.56 2.3 Hz, arom. C), 132.31 (d, J ϭ 8.9 Hz, arom. C), 134.11 (dd, J ϭ
(d, J ϭ 5.7 Hz, arom. C), 25.22 (d, J ϭ 3.2, arom. C), 124.72 (s,
arom. C), 124.47 (s, arom. C), 124.36 (d, J ϭ 2.2 Hz, arom. C),
1.0, 1.0 Hz, arom. C), 145.91 (d, J ϭ 14.8 Hz, arom. C) ppm.
31P{1H} NMR (CD2Cl2): δ ϭ 25.19 (d, J ϭ 150.4 Hz), Ϫ141.0
124.00 (s, arom. C), 123.03 (d, J ϭ 1.0 Hz, arom. C), 58.16 (d, J ϭ (sept, J ϭ 710.6 Hz) ppm. C24H38F6NP2Rh (619.4): calcd. C 46.54,
7.9 Hz, NMe), 38.38 (d, J ϭ 5.0 Hz, CH), 7.83 (d, J ϭ 3.1 Hz, Me) H 6.18, N 2.26, P 10.00; found C 46.55, H 6.11, N 2.37, P 10.36.
ppm. 31P{1H} NMR (C6D6): δ ϭ 150.2 ppm. MS (EI): m/z ϭ 463
Isomer (S,RR)-7b: [α]2D0 ϭ Ϫ100.3 (c ϭ 1.1, CH2Cl2). 1H NMR
(CD3COCD3): δ ϭ 0.89 (dd, J ϭ 6.9, 14.2 Hz, 3 H, Me), 1.41 (m,
1 H, CH2), 1.55 (m, 1 H, CH2), 1.65 (m, 1 H, CH2), 1.84 (dd, 3 H,
J ϭ 7.0, 18.2 Hz, Me), 1.91 (m, 1 H, CH2), 2.07 (m, 1 H, CH),
2.13 (m, 1 H, CH2), 2.22 (d, J ϭ 6.6 Hz, 3 H, Me), 2.37 (m, 1 H,
[Mϩ]. C30H26NO2P (463.5): calcd. C 77.74, H 5.65, N 3.02, P 6.68;
found.: C 77.48, H 5.76, N 3.12, P 6.82.
RhI Complexes 7a and 7b: Either (S,RR)-5 or (R,RR)-5 (0.10 g,
0.38 mmol) was added to a solution of [Rh(1,5-cyclooctadiene)Cl]2
(93.7 mg, 0.19 mmol) or [Rh(2,5-norbornadiene)Cl]2 (87.6 mg, CH2), 2.58 (s, 3 H, NMe), 2.86 (m, 1 H, CH), 2.87 (s, 3 H, NMe),
0.19 mmol) in dichloromethane (5 mL). The reaction mixture was
stirred at ambient temperature for 20 min. A solution of KPF6
3.74 (dq, J ϭ 1.6, 6.6 Hz, 1 H, CH), 4.02 (m, 1 H, CH), 4.05 (m,
1 H, olef. H), 4.10 (m, 1 H, CH), 4.16 (m, 1 H, olef. H), 5.43 (m,
(105 mg, 0.57 mmol) in water (5 mL) was added with stirring after 1 H, olef. H), 5.67 (m, 1 H, olef. H), 7.29 (m, 1 H, arom. H), 7.49
1 h. The aqueous phase was separated and the organic phase was
washed with three aliquots of water (10 mL). After addition of a
tenfold amount of diethyl ether, the Rh complexes were precipi-
tated as red, crystalline solids in 90Ϫ95% yield. Crystals of (S,RR)-
(m, 1 H, arom. H), 7.52 (m, 1 H, arom H), 7.73 (m, 1 H, arom. H)
ppm. 13C{1H} NMR (CD3COCD3): δ ϭ 14.31 (d, J ϭ 2.0 Hz, Me),
18.91 (dd, J ϭ 1.0, 10.7 Hz, Me), 24.35 (d, J ϭ 3.8 Hz, Me), 33.17
(dd, J ϭ 1.8, 28.0 Hz, CH), 36.67 (dd, J ϭ 1.4, 1.4 Hz, CH2), 38.34
and (R,RR)-7a suitable for X-ray structural analysis could be ob- (d, J ϭ 4.3, CH2), 44.91 (dd, J ϭ 1.4, 26.6 Hz, CH), 50.65 (d, J ϭ
tained by slow concentration of the dichloromethane solutions.
2.8 Hz, NMe), 51.70 (s, NMe), 52.30 (dd, J ϭ 2.0, 2.0 Hz, CH),
53.58 (dd, J ϭ 1.3, 2.8 Hz, CH), 56.28 (d, J ϭ 9.9 Hz, olef. C),
63.74 (d, J ϭ 10.7 Hz, olef. C), 66.61 (dd, J ϭ 1.7, 5.2 Hz, CH2),
73.34 (d, J ϭ 5.1 Hz, CH), 87.55 (dd, J ϭ 5.3, 10.4 Hz, olef. C),
92.20 (dd, J ϭ 6.2, 8.0 Hz, olef. C), 124.66 (d, J ϭ 24.2 Hz, arom.
C), 129.95 (d, J ϭ 5.3 Hz, arom. C), 132.25 (d, J ϭ 9.4 Hz, arom.
C), 132.73 (d, J ϭ 2.3 Hz arom. C), 136.08 (dd, J ϭ 1.3, 1.3 Hz,
arom. C), 148.52 (d, J ϭ 15.3 Hz, arom. C) ppm. 31P{1H} NMR
(CD3COCD3): δ ϭ 32.43(d,167.9 Hz), Ϫ143.0 (sept, J ϭ 707.4 Hz)
ppm. C23H34F6NP2Rh (603.4): calcd. C 45.78, H 5.68, N 2.32, P
10.27; found C 45.60, H 5.59, N 2.30, P 10.05.
Isomer (S,RR)-7a: [α]2D0 ϭ 13.7 (c ϭ 1.1, CH2Cl2). 1H NMR
(CD2Cl2): δ ϭ 0.91 (dd, J ϭ 6.4, 15.0 Hz, 3 H, Me), 1.81 (m, 1 H,
CH2), 1.82 (dd, J ϭ 6.9, 18.1 Hz, 3 H, Me), 1.97 (m, 1 H, CH2),
2.20 (m, 2 H, CH/CH2), 2.26 (d, J ϭ 6.5 Hz, 3 H, Me), 2.34 (s, 3
H, NMe), 2.40 (m, 1 H, CH), 2.53 (m, 1 H, CH2), 2.70 (s, 3 H,
NMe), 2.75 (m, 1 H), 2.87 (m, 1 H,), 3.31 (m, 1 H, olef. H), 3.56
(d, J ϭ 6.5 Hz, 1 H, CH), 4.10 (m, 1 H, olef. H), 5.95 (m, 1 H,
olef. H), 5.44 (m, 1 H, olef. H), 7.18 (m, 1 H, arom. H), 7.49 (m,
2 H, arom. H), 7.61 (m, 1 H, arom. H) ppm. 13C{1H} NMR
(CD2Cl2): δ ϭ14.05 (d, J ϭ 0.8 Hz, Me), 19.62 (d, J ϭ 9.7 Hz,
Me), 23.92 (d, J ϭ 5.6 Hz, Me), 26.03 (d, J ϭ 2.5 Hz, CH2), 28.90
Isomer (R,RR)-7b: [α]2D0 ϭ Ϫ78.1 (c ϭ 1.1, CH2Cl2). 1H NMR
(d, J ϭ 1.3 Hz, CH2), 32.47 (s, CH2), 33.46 (dd, J ϭ 25.9, 1.0 Hz, (CD3COCD3): δ ϭ 1.18 (dd, J ϭ 7.2, 14.2 Hz, 3 H, Me), 1.29 (m,
CH), 35.63 (d, J ϭ 3.8 Hz, CH2), 36.05 (dd, J ϭ 1.4, 1.4 Hz, CH2), 1 H, CH2), 1.54 (m, 1 H, CH2), 1.64 (m, 1 H, CH2), 1.64 (dd, J ϭ
38.11 (d, J ϭ 2.3 Hz, CH2), 44.14 (dd, J ϭ 26.5, 1.3 Hz, CH), 51.57 7.1, 17.6 Hz, 3 H, Me), 1.87 (d, J ϭ 0.5 Hz, 3 H, 6.6 Hz, Me), 1.95
(d, J ϭ3.4 Hz, NMe), 52.19 (s, NMe), 68.54 (dd, J ϭ 12.1, 1.0 Hz, (m, 1 H, CH2), 2.23 (m, 1 H, CH), 2.27 (m, 1 H, CH), 2.54 (s, 3
olef. C), 73.64 (d, J ϭ 6.1 Hz, CH), 81.72 (d, J ϭ 12.5 Hz, olef. C), H, NMe), 2.57 (m, 1 H, CH), 2.59 (s, 3 H, NMe), 2.61 (m, 1 H,
100.41 (dd, J ϭ 13.0, 7.1 Hz, olef. C), 106.06 (d, J ϭ 8.4, 6.10 Hz,
olef. C), 124.91 (d, J ϭ 23.9 Hz, arom. C), 129.71 (d, J ϭ 4.8 Hz,
CH), 3.64 (dq, J ϭ 1.9, 6.6 Hz, 1 H, CH), 4.03 (m, 1 H, olef. H),
4.05 (m, 1 H, olef. H), 4.21 (m, 1 H, CH.), 4.32 (m, 1 H, CH), 5.38
arom. C), 131.73 (d, J ϭ 8.9 Hz, arom. C), 132.33 (d, J ϭ 2.3 Hz, (m, 1 H, olef. H), 5.58 (m, 1 H, olef. H), 7.30 (m, 1 H, arom. H),
arom. C), 134.84 (dd, J ϭ 1.1, 1.1 Hz, arom. C), 146.43 (d, J ϭ
7.48 (m, 1 H, arom. H), 7.52 (m, 1 H, arom H), 7.65 (m, 1 H,
14.8 Hz, arom. C) ppm. 31P{1H} NMR (CD2Cl2): δ ϭ 28.30 (d, arom. H) ppm. 13C{1H} NMR (CD3COCD3): δ ϭ 14.80 (d, J ϭ
J ϭ 150.4 Hz), Ϫ143.2 (sept, J ϭ 710.6 Hz) ppm. C24H38F6NP2Rh 2.53 Hz, Me), 18.15 (dd, J ϭ 1.8, 8.1 Hz, Me), 26.65 (d, J ϭ 3.8 Hz,
(619.4): calcd. C 46.54, H 6.18, N 2.26, P 10.00; found C 46.70, H
6.32, N 2.39, P 10.38.
Me), 35.46 (dd, J ϭ 1.5, 27.0 Hz, CH), 37.11 (dd, J ϭ 1.5, 1.5 Hz,
CH2), 38.51 (d, J ϭ 4.1, CH2), 46.51 (dd, J ϭ 1.8, 26.2 Hz, CH),
49.64 (d, J ϭ 1.8 Hz, NMe),51.57 (s, NMe), 53.55 (dd, J ϭ 2.0,
2.0 Hz, CH),53.82 (dd, J ϭ 1.3, 2.8 Hz, CH), 56.40 (d, J ϭ 9.9 Hz,
olef. C), 65.66 (d, J ϭ 11.2 Hz, olef. C), 67.58 (dd, J ϭ 1.8, 5.3 Hz,
CH2), 72.95 (dd, J ϭ 5.6, CH), 87.22 (dd, J ϭ 5.6, 9.7 Hz, olef. C),
92.01 (dd, J ϭ 6.1, 8.9 Hz, olef. C), 125.17 (d, J ϭ 23.9 Hz, arom.
C), 130.73 (d, J ϭ 5.1 Hz, arom. C), 133.13 (d, J ϭ 9.2 Hz, arom.
C), 133.20 (d, J ϭ 2.3 Hz, arom. C), 136.38 (dd, J ϭ 1.3, 1.3 Hz,
arom. C), 148.80 (d, J ϭ 15.3 Hz, arom. C) ppm. 31P{1H} NMR
Isomer (R,RR)-7a: [α]2D0 ϭ 21.5 (c ϭ 1.0, CH2Cl2). 1H NMR
(CD2Cl2): δ ϭ 1.29 (dd, 3 H, J ϭ 7.1, 14.2 Hz, Me), 1.49 (m, 1 H,
CH2), 1.70 (dd, 3 H, J ϭ 7.1, 17.3 Hz, Me), 1.83 (d, J ϭ 6.5 Hz, 3
H, Me), 2.09 (m, 2 H, CH2), 2.23 (m, 1 H, CH2), 2.41 (m, 1 H,
CH), 2.58 (s, 3 H, NMe), 2.60 (m, 1 H, CH), 2.69 (s, 3 H, NMe),
3.47 (q, J ϭ 6.5 Hz, 1 H CH), 3.58 (m, 1 H, olef. H), 4.15 (m, 1
H, olef. H), 4.93 (m, 1 H, olef. H), 5.50 (m, 1 H, olef. H), 7.0 (m,
1 H, arom. H), 7.48 (m, 2 H, arom. H), 7.60 (m, 1 H, arom. H)
ppm. 13C{1H} NMR (CD2Cl2): δ ϭ13.54 (d, J ϭ 1.3 Hz, Me),
18.02 (d, J ϭ 6.6 Hz, Me), 25.89 (d, J ϭ 4.1 Hz, Me), 27.96 (d,
J ϭ 2.0 Hz, CH2), 30.31 (s, CH2), 31.07 (d, J ϭ 2.5 Hz, CH2), 33.51
(d, J ϭ 3.1 Hz, CH2), 35.68 (dd, J ϭ 25.2, 1.0 Hz, CH2), 35.95 (dd,
(CD3COCD3):
δ ϭ 28.74 (d,167.9 Hz), Ϫ143.0 (sept, J ϭ
707.4 Hz). C23H34F6NP2Rh (603.4): calcd. C 45.78, H 5.68, N 2.32,
P 10.27; found C 45.56, H 5.85, N 2.35, P 10.17.
Asymmetric Hydrogenation Reactions: A 100-mL glass autoclave
J ϭ 1.7, 1.7 Hz, CH2), 38.35 (d, J ϭ 2.0 Hz, CH), 45.93 (dd, J ϭ was charged with a solution of methyl (Z)-α-acetamidocinnamate
25.6, 1.7 Hz, CH), 49.75 (d, J ϭ 2.5 Hz, NMe), 51.11 (s, NMe), (8, 0.40 g, 1.8 mmol) in methanol (15 mL). After repeated vacuum/
69.52 (dd, J ϭ 11.8, 0.9 Hz, olef. C), 73.15 (d, J ϭ 5.9 Hz, CH), H2 cycles, the catalyst (ca. 1 mol %) was added and the autoclave
81.70 (dd, J ϭ 13.1, 0.9 Hz, olef. C), 101.33 (dd, J ϭ 11.6, 7.3 Hz, was pressurised to 5 bar with hydrogen. The reactions were allowed
Eur. J. Inorg. Chem. 2003, 1748Ϫ1755
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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