Chiral Phosphine−Olefin Ligands
A R T I C L E S
13C NMR (CDCl3): δ 146.1 (d,3JCP ) 3.6 Hz) 144.43 (d,1JCP ) 30.0
Hz), 144.38 (d,1JCP ) 29.0 Hz), 143.61 (d,2JCP ) 8.8 Hz), 143.60 (d,2JCP
) 9.4 Hz), 135.4, 130.4 (d,2JCP ) 14.4 Hz), 130.2 (d,2JCP ) 13.9 Hz),
128.6, 128.2 (d,3JCP ) 3.5 Hz), 128.1, 127.2, 126.97 (d,3JCP ) 7.3 Hz),
126.96 (d,3JCP ) 7.8 Hz), 125.2, 121.18, 121.15, 63.1 (d,1JCP ) 10.9
for the first time in observing a negative nonlinear effect derived
from an inactive trimer-active monomer equilibrium of the
catalyst.
Experimental Section
Hz), 47.3 (d,2JCP ) 9.9 Hz), 47.2 (d,2JCP ) 10.4 Hz), 27.4 (d,3JCP
)
General. All air- and moisture-sensitive manipulations were carried
out with standard Schlenk techniques under nitrogen or in a glove box
under argon. Benzene, hexane, and 1,4-dioxane were distilled over
benzophenone ketyl under nitrogen. Dichloromethane was distilled over
CaH2 under nitrogen. Phosphine-olefins 1a and 1f were synthesized
following the literature procedures.8 Phosphine-olefins 1b-1e were
synthesized in a similar manner following the procedure for 1a.8 [Rh-
4.1 Hz), 25.4 (d,3JCP ) 4.1 Hz). 31P{1H} NMR (CDCl3): δ -16.5 (s).
[R]20D -428 (c 0.16, CH2Cl2). HRMS (ESI) calcd for C25H22P (M+H+)
353.1454, found 353.1456.
(1S,4R,7S)-(-)-7-Diphenylphosphino-2-(3,5-dimethylphenyl)bicyclo-
[2.2.1]hept-2-ene (1e): 1H NMR (CDCl3): δ 7.39 (t,3J ) 7.3 Hz, 2H),
7.33-7.27 (m, 8H), 7.02 (s, 2H), 6.86 (s, 1H), 6.28 (d,3JHH ) 2.8 Hz,
1H), 3.18 (s, 1H), 2.95 (s, 1H), 2.48 (d,2JPH ) 6.9 Hz, 1H), 2.29 (s,
6H), 1.92-1.83 (m, 2H), 1.32-1.24 (m, 2H). 13C NMR (CDCl3): δ
24
8
(OH)(cod)]2 and [RhCl((7S)-1a)]2 were synthesized following the
literature procedures.
146.6 (d,3JCP ) 3.5 Hz), 139.8 (d,1JCP ) 43.9 Hz), 139.6 (d,1JCP
)
Analytical Data for Phosphine-Olefins 1. (1S,4R,7S)-(-)-7-
43.4 Hz), 137.8, 135.2, 133.0 (d,2JCP ) 19.7 Hz), 132.9 (d,2JCP ) 19.2
Hz), 128.8, 128.3 (d,3JCP ) 6.1 Hz), 128.23, 128.21 (d,3JCP ) 6.1 Hz),
128.20, 127.8 (d,3JCP ) 4.1 Hz), 123.1, 62.1 (d,1JCP ) 4.8 Hz), 55.09,
55.08, 47.0 (d,2JCP ) 10.9 Hz), 46.9 (d,2JCP ) 10.9 Hz), 27.9 (d,3JCP
) 3.1 Hz), 25.9 (d,3JCP ) 4.1 Hz). 31P{1H} NMR (CDCl3): δ -17.2
(s). [R]20D -249 (c 0.43, CH2Cl2). Anal. Calcd for C27H27P: C, 84.79;
H, 7.12. Found: C, 85.04; H, 6.96.
Diphenylphosphino-2-phenylbicyclo[2.2.1]hept-2-ene (1a): 1H NMR
(CDCl3): δ 7.45-7.35 (m, 5H), 7.35-7.22 (m, 9H), 7.19 (t,3JHH
)
7.3 Hz, 1H), 6.31 (d,3JHH ) 2.8 Hz, 1H), 3.18 (s, 1H), 2.97 (s, 1H),
2.49 (d,3JHH ) 6.8 Hz, 1H), 1.95-1.80 (m, 2H), 1.33-1.20 (m, 2H).
13C NMR (CDCl3): δ 146.4 (d,3JCP ) 4.1 Hz), 139.7 (d,1JCP ) 48.7
Hz), 139.6 (d,1JCP ) 48.5 Hz), 135.4, 133.0 (d,2JCP ) 19.1 Hz), 132.9
(d,2JCP ) 19.2 Hz), 128.40, 128.35, 128.29 (d,3JCP ) 2.5 Hz), 128.28
(d,3JCP ) 3.1 Hz), 128.2, 128.1 (3JCP ) 3.6 Hz), 127.0, 125.3, 61.8
(d,1JCP ) 5.1 Hz), 47.2 (d,2JCP ) 6.6 Hz), 47.1 (d,2JCP ) 6.6 Hz), 27.8
(d,3JCP ) 3.6 Hz), 25.9 (d,3JCP ) 4.1 Hz). 31P{1H} NMR (CDCl3): δ
-17.1 (s). [R]20D -287 (c 0.40, CH2Cl2). Anal. Calcd for C25H23P: C,
84.72; H, 6.54. Found: C, 84.77; H, 6.79.
(1S,4R,7S)-(-)-7-Diphenylphosphino-2-benzylbicyclo[2.2.1]hept-
1
2-ene (1f): H NMR (CDCl3): δ 7.38-7.34 (m, 2H), 7.32-7.17 (m,
11H), 7.12-7.09 (m, 2H), 5.59 (s, 1H), 3.44 (d,2JHH ) 15.3 Hz, 1H),
3.40 (d,2JHH ) 15.4 Hz, 1H), 2.79 (s, 1H), 2.52 (s, 1H), 2.28 (d,3JHH
)
7.2 Hz, 1H), 1.82-1.74 (m, 1H), 1.65-1.58 (m, 1H), 1.25-1.16 (m,
1H), 1.05-0.95 (m, 1H). 13C NMR (CDCl3): δ 147.0 (d,3JCP ) 3.1
Hz), 139.9 (d,1JCP ) 43.9 Hz), 139.7 (d,1JCP ) 43.4 Hz), 139.2, 133.0
(d,2JCP ) 19.1 Hz), 132.7 (d,2JCP ) 19.2 Hz), 129.37, 129.36, 128.24
(d,3JCP ) 6.1 Hz), 128.23, 128.13 (d,3JCP ) 4.1 Hz), 128.09, 127.9
(3JCP ) 4.1 Hz), 125.9, 62.2 (d,1JCP ) 5.1 Hz), 48.5 (d,2JCP ) 12.4
Hz), 46.3 (d,2JCP ) 12.9 Hz), 36.9, 27.9 (d,3JCP ) 3.6 Hz), 25.6 (d,3JCP
) 4.1 Hz). 31P{1H} NMR (CDCl3): δ -17.5 (s). [R]20D -56.5 (c 0.56,
CH2Cl2). Anal. Calcd for C26H25P: C, 84.75; H, 6.84. Found: C, 84.96;
H, 7.10.
(1S,4R,7S)-(-)-7-Di(4-methoxyphenyl)phosphino-2-phenylbicyclo-
1
[2.2.1]hept-2-ene (1b): H NMR (CDCl3): δ 7.39 (d,3JHH ) 7.4 Hz,
2H), 7.34 (dd,3JHH ) 8.5 Hz and3JPH ) 7.0 Hz, 2H), 7.29 (t,3JHH ) 7.5
Hz, 2H), 7.25 (dd,3JHH ) 8.6 Hz and3JPH ) 7.4 Hz, 2H), 7.20 (t,3JHH
) 7.3 Hz, 1H), 6.88 (d,3JHH ) 8.7 Hz, 2H), 6.83 (d,3JHH ) 8.8 Hz,
2H), 6.30 (d,3JHH ) 3.0 Hz, 1H), 3.80 (s, 3H), 3.78 (s, 3H), 3.16 (s,
1H), 2.94 (s, 1H), 2.43 (d,2JPH ) 6.9 Hz, 1H), 1.93-1.81 (m, 2H),
1.31-1.24 (m, 2H). 13C NMR (CDCl3): δ 159.8, 146.3 (d,3JCP ) 3.5
Hz), 135.3, 134.2 (d,2JCP ) 21.2 Hz), 134.1(d,2JCP ) 20.2 Hz), 130.6
Preparation of [Rh3(µ-O)(µ-OH)((7S)-1a)3] (6). A mixture of [Rh-
(OH)(cod)]2 (68.4 mg, 0.300 mmol Rh) and (7S)-1a (106 mg, 0.300
mmol) in benzene (15 mL) was stirred for 5 h at 50 °C, and the solvent
was removed under vacuum. The residue was dissolved in dichlo-
romethane (8 mL) and filtered through PTFE membrane (0.45 µm).
The remaining solution was diluted with hexane (30 mL) to form a
precipitate, and it was collected by filtering off the solvent and dried
under vacuum to afford an orange solid (100 mg, 0.071 mmol, 71%
yield), which was further recrystallized from dichloromethane/hexane
to furnish single crystals suitable for X-ray analysis.
(d,1JCP ) 61.6 Hz), 130.5 (d,1JCP ) 60.4 Hz), 128.3, 128.1 (d,3JCP
)
3.6 Hz), 126.9, 125.2, 114.0 (d,3JCP ) 7.3 Hz), 113.9 (d,3JCP ) 7.8
Hz), 62.1 (d,1JCP ) 4.8 Hz), 55.09, 55.08, 47.0 (d,2JCP ) 10.9 Hz),
46.9 (d,2JCP ) 10.9 Hz), 27.9 (d,3JCP ) 3.1 Hz), 25.9 (d,3JCP ) 4.1
Hz). 31P{1H} NMR (CDCl3): δ -20.9 (s). [R]20D -263 (c 0.40, CH2-
Cl2). Anal. Calcd for C27H27O2P: C, 78.24; H, 6.57. Found: C, 78.05;
H, 6.66.
(1S,4R,7S)-(-)-7-Di(4-trifluoromethylphenyl)phosphino-2-
phenylbicyclo[2.2.1]hept-2-ene (1c): 1H NMR (CDCl3): δ 7.59 (d,3JHH
) 7.8 Hz, 2H), 7.53 (d,3JHH ) 7.8 Hz, 2H), 7.49 (t,3J ) 7.1 Hz, 2H),
1H NMR (C6D6): δ 8.45 (dd,3JHH ) 10.5 and 8.3 Hz, 6H), 8.11
7.40 (t,3J ) 7.0 Hz, 2H), 7.37 (d,3JHH ) 8.4 Hz, 2H), 7.31 (t,3JHH
)
(dd,3JHH ) 10.7 and 8.4 Hz, 6H), 7.30-7.10 (m, 15H), 6.85 (t,3JHH
)
7.4 Hz, 2H), 7.23 (t,3JHH ) 7.1 Hz, 1H), 6.32 (d,3JHH ) 2.4 Hz, 1H),
3.19 (s, 1H), 2.99 (s, 1H), 2.49 (d,2JPH ) 6.6 Hz, 1H), 1.99-1.87 (m,
7.5 Hz, 3H), 6.79 (t,3JHH ) 7.3 Hz, 6H), 6.63 (t,3JHH ) 6.9 Hz, 3H),
6.55 (t,3JHH ) 7.1 Hz, 6H), 3.33 (s, 3H), 2.94 (s, 3H), 2.76 (s, 3H),
1.82-1.76 (m, 3H), 1.68 (s, 3H), 1.57-1.52 (m, 3H), 1.41-1.28 (m,
6H), -3.10 (s, 1H). 31P{1H} NMR (C6D6): δ 73.2 (d,1JRhP ) 211 Hz).
Anal. Calcd for C75H67O2P3Rh3: C, 64.25; H, 4.82. Found: C, 64.52;
H, 5.06.
2H), 1.40-1.28 (m, 2H). 13C NMR (CDCl3): δ 146.7, 144.2 (d,1JCP
)
23.8 Hz), 144.0 (d,1JCP ) 21.2 Hz), 134.9, 133.2 (d,2JCP ) 20.7 Hz),
133.0 (d,2JCP ) 20.2 Hz), 130.6 (q,2JCF ) 32.1 Hz), 128.5, 127.8 (d,3JCP
) 3.6 Hz), 127.3, 125.1, 124.1 (q,1JCF ) 271.2 Hz), 61.5 (d,1JCP ) 5.1
Hz), 47.3, 47.2, 27.6 (d,3JCP ) 3.6 Hz), 25.7 (d,3JCP ) 3.1 Hz). 31P-
{1H} NMR (CDCl3): δ -15.7 (s). [R]20D -214 (c 0.65, CH2Cl2). Anal.
Calcd for C27H21F6P: C, 66.12; H, 4.32. Found: C, 66.21; H, 4.47.
(1S,4R,7S)-(-)-7-Dibenzophosphoryl-2-phenylbicyclo[2.2.1]hept-
General Procedure for Rh/(7S)-1a-Catalyzed Asymmetric 1,4-
Addition (Tables 1 and 2). KOH (0.10 mL, 0.10 mmol; 1.0 M
aqueous) was added to a solution of [RhCl((7S)-1a)]2 (4.9 mg, 10 mmol
Rh) in 1,4-dioxane (0.50 mL), and the resulting solution was stirred
for 5 min at room temperature. ArB(OH)2 (0.60 mmol) and an R,â-
unsaturated compound (0.20 mmol) were then added to it with
additional 1,4-dioxane (0.50 mL), and the resulting mixture was stirred
for 3 h at 50 °C. After passing through a pad of silica gel with EtOAc,
the solvent was removed under vacuum. The residue was chromato-
graphed on silica gel with EtOAc/hexane to afford the 1,4-adduct.
1
2-ene (1d): H NMR (CDCl3): δ 7.90 (d,3JHH ) 7.7 Hz, 1H), 7.89
(d,3JHH ) 7.8 Hz, 1H), 7.76 (dd,3JHH ) 7.5 Hz and3JPH ) 4.5 Hz, 1H),
7.63 (dd,3JHH ) 6.8 Hz and3JPH ) 4.6 Hz, 1H), 7.56 (d,3JHH ) 7.7 Hz,
2H), 7.44 (t,3JHH ) 7.3 Hz, 1H), 7.42 (t,3JHH ) 7.2 Hz, 1H), 7.39 (t,3JHH
) 7.7 Hz, 2H), 7.37-7.33 (m, 1H), 7.31-7.29 (m, 1H), 7.28 (t,3JHH
)
7.4 Hz, 1H), 6.47 (d,3JHH ) 3.0 Hz, 1H), 3.49 (s, 1H), 3.23 (s, 1H),
1.71-1.63 (m, 2H), 1.58 (d,2JPH ) 6.2 Hz, 1H), 1.32-1.23 (m, 2H).
Acknowledgment. Support has been provided in part by a
(24) Uson, R.; Oro, L. A.; Cabeza, J. A. Inorg. Synth. 1985, 23, 126.
Grant-in-Aid for Scientific Research, the Ministry of Education,
9
J. AM. CHEM. SOC. VOL. 129, NO. 7, 2007 2137