1908
A. Korostyle6 et al. / Tetrahedron: Asymmetry 14 (2003) 1905–1909
1
uum. The white solid obtained represented pure
chlorophosphite 3a (31P NMR: l 178.7) and was used
in the second step without further purification.
l 129.05. H NMR (CDCl3): l 7.05 (m, 4H), 6.96 (m,
4H), 2.80 (m, 8H), 2.64 (m, 4H), 2.27 (m, 4H), 1.77 (m,
12H), 1.55 (m, 4H). EI-HRMS (70 eV): 662.2336 (calcd
for C40H40O5P2: 662.2351).
A solution of degassed water (0.065 ml, 3.5 mmol) in
THF (10 ml) was slowly added to a vigorously stirred
solution of the chlorophosphite 3a (7.0 mmol) and
triethylamine (1.2 ml, 8.6 mmol) in THF (40 ml). After
the mixture had been stirred for additional 2 h, a white
precipitate was filtered off and washed with THF (15
ml). The combined filtrates were concentrated in vac-
uum to give a beige amorphous solid, which was
purified by flash chromatography (silica gel, CH2Cl2).
White solid, 1.72 g (72% yield). Mp 170°C. EI-MS (70
eV): 646 (100%) [M]+. [h]D23=−456.7 (c 0.79, CH2Cl2).
31P NMR (CDCl3): l 137.1. 13C NMR (CDCl3): l 121.8
(CH), 122.0 (CH), 123.2 (C), 124.5 (C), 125.1, 125.4,
126.3, 126.5, 127.1, 127.2, 128.5, 128.6, 130.0, 130.6,
131.4, 131.8, 132.6, 132.9 (CH), 147.1 (C), 147.4 (C). 1H
NMR (CDCl3): l 7.27 (m, 6H), 7.41 (m, 10H), 7.55 (d,
J=8.8 Hz, 2H), 7.89 (m, 6H). Found: C, 73.60; H, 3.50.
Calcd for C40H24O5P2: C, 74.29; H, 3.74.
3.6. Preparation of Rh complexes with ligands 4a–d
(general procedure)
A solution of a corresponding ligand (0.18 mmol) in
CH2Cl2 (10 ml) was added dropwise to a stirred solu-
tion of [Rh(COD)2]BF4 (0.073 g, 0.18 mmol) in CH2Cl2
(20 ml) at 20°C. The reaction mixture was stirred for 30
min, concentrated in vacuum, and 10 ml of hexane was
added to the residue. The obtained solid rhodium com-
plex was washed with hexane (2×10 ml) and dried in
vacuum.
3.7. Catalytic hydrogenations (general procedure)
The prochiral olefin (1 mmol) was dissolved in CH2Cl2
(13 ml) under hydrogen atmosphere. A rhodium precat-
alyst (0.01 mmol) was subsequently added and the
reaction mixture vigorously stirred under hydrogen (1
atm) at 25°C until the calculated amount of H2 had
been consumed. Both conversion and enantioselectivity
of hydrogenation were then determined by GC.
3.3. Bis(3,3%-dimethyl-1,1%-binaphthyl-2,2%-ene)-pyrophos-
phite 4b
Application of the same method as detailed above for
the synthesis of 4a, starting from 0.63 g (2.0 mmol) of
(R)-3,3%-dimethyl-2,2%-dihydroxy-1,1%-binaphthyl
2b.
Acknowledgements
For the intermediate chlorophosphite 3b: 31P NMR
(CDCl3): l 174.8. White solid, 0.49 g (70% yield). Mp
244–245°C. EI-MS (70 eV): 702 (100%) [M]+. [h]D22=
−421.1 (c 0.45, CH2Cl2). 31P NMR (CDCl3): l 137.7.
1H NMR (CDCl3): l 7.83 (m, 6H), 7.42 (m, 6H), 7.22
(m, 8H), 2.51 (s, 6H, CH3), 2.12 (s, 6H, CH3). EI-
HRMS (70 eV): 702.1766 (calcd for C44H32O5P2:
702.1725). Found: C, 73.93; H, 4.66. Calcd for
C44H32O5P2: C, 75.20; H, 4.59.
Financial support from Degussa AG is gratefully
acknowledged. The authors wish to thank Mrs. K.
Buchholz for skilled technical assistance and Mrs. S.
Buchholz for the performance of GC analyses.
References
3.4. Bis(3,3%-dibromo-1,1%-binaphthyl-2,2%-ene)-pyrophos-
phite 4c
1. Organic Phosphorus Compounds; Kosolapoff, G. M.;
Maier, L., Eds.; John Wiley: New York, 1973; Vol. 5; p.
196.
Application of the same method as detailed above for
the synthesis of 4a, starting from 0.66 g (1.5 mmol) of
(R)-3,3%-dibromo-2,2%-dihydroxy-1,1%-dinaphthyl 2c. For
the intermediate chlorophosphite 3c: 31P NMR
(CDCl3): l 181.1. White solid, 0.49 g (69% yield). Mp
150°C. EI–MS (70 eV): 958 (25%) [M]+, 879 (100%)
[M−Br]+. [h]2D3=−509.4 (c 0.57, CH2Cl2). 31P NMR
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3. Alvarez, M. A.; Alvarez, C.; Garcia, M. E.; Riera, V.;
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1
(CDCl3): l 138.7. H NMR (CDCl3): l 8.21 (s, 2H),
8.07 (s, 2H), 7.79 (m, 4H), 7.43 (m, 4H), 7.21 (m, 8H).
Found: C, 50.25; H, 2.48. Calcd for C40H20Br4O5P2: C,
50.12; H, 2.10.
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Corp.), US 5,858,905 (12.01.1999).
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3.5. Bis(5,5%,6,6%,7,7%,8,8%-octahydro-1,1%-binaphthyl-2,2%-
ene)-pyrophosphite 4d
Application of the same method as detailed above for
the synthesis of 4a, starting from 0.59 g (2.0 mmol) of
(R)-H8-BINOL 2d. For the intermediate chlorophos-
phite 3d: 31P NMR (CDCl3): l 169.2. White solid, 0.15
g (22% yield). Mp 150°C. EI–MS (70 eV): 662 (100%)
[M]+. [h]2D2=−198.8 (c 0.5, CH2Cl2). 31P NMR (CDCl3):
7. DeBellis, A. D.; Pastor, S. D.; Rihs, G.; Rodebaugh, R.
K.; Smith, A. R. Inorg. Chem. 2001, 40, 2156–2160.