Synthesis of novel chiral phosphines from α,α-trehalose

Article abstract of DOI:10.1016/S0957-4166(99)00430-9

New disaccharide chiral phosphines, such as 4,6-O-benzylidene-2- (diphenylphosphino)-2-deoxy-α-D-altropyranosyl-(1,1)-4,6-O-benzylidene-2- (diphenylphosphino)-2-deoxy-α-D-altropyranoside 1 and 2-(diphenylphosphino)- 2-deoxy-4,6-O-isopropylidene-α-D-altropyranosyl-(1,1)-2-(diphenylphosphino)- 2-deoxy-4,6-O-isopropylidene-α-D-altropyranoside 9, were prepared from α,α-trehalose. We also succeeded in the synthesis of polyhydroxy chiral diphosphine 2-(diphenylphosphino)-2-deoxy-α-D-altropyranosyl-(1,1)-2- (diphenylphosphino)-2-deoxy-α-D-altropyranoside 5 by deprotection of isopropylidene groups.

Full text of DOI:10.1016/S0957-4166(99)00430-9

Pergamon
Tetrahedron: Asymmetry 10 (1999) 4029–4035
Synthesis of novel chiral phosphines from α,α-trehalose
Koji Yonehara, Tomohiro Hashizume, Kouichi Ohe ∗ and Sakae Uemura ∗
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University,
Sakyo-ku, Kyoto 606-8501, Japan
Received 8 September 1999; accepted 25 September 1999
Abstract
New disaccharide chiral phosphines, such as 4,6-O-benzylidene-2-(diphenylphosphino)-2-deoxy-α-D-altro-
pyranosyl-(1,1)-4,6-O-benzylidene-2-(diphenylphosphino)-2-deoxy-α-D-altropyranoside 1 and 2-(diphenylphos-
phino)-2-deoxy-4,6-O-isopropylidene-α-D -altropyranosyl-(1,1)-2-(diphenylphosphino)-2-deoxy-4,6-O-isoprop-
ylidene-α-D-altropyranoside 9, were prepared from α,α-trehalose. We also succeeded in the synthesis of
polyhydroxy chiral diphosphine 2-(diphenylphosphino)-2-deoxy-α-D-altropyranosyl-(1,1)-2-(diphenylphos-
phino)-2-deoxy-α-D-altropyranoside 5 by deprotection of isopropylidene groups. © 1999 Elsevier Science Ltd.
All rights reserved.
1. Introduction
The design and synthesis of chiral ligands are of significant importance in the development of transition
metal-catalyzed asymmetric reactions.1 Carbohydrates, especially monosaccharides, have received a
great deal of attention as a chiral source of ligands, because they exist widely in nature and have
some advantages for asymmetric synthesis, such as ready availability and many stereogenic centers
in their skeletons. While many phosphine and phosphinite ligands derived from monosaccharides have
been reported,2 the types of chiral phosphines in which the phosphorus atoms are attached directly to
the secondary carbons of a sugar are few in number. They are somewhat difficult to make, since the
introduction of a phosphorus atom on the secondary carbon of sugars by the nucleophilic replacement
competes with undesired elimination reactions. Recently, the groups of Wardell3 and Shi4 reported the
preparation of 2- and 3-phosphinosugars in high yields by the nucleophilic ring-opening reactions of
methyl 2,3-anhydro-4,6-O-benzylidene-α-D-allopyranoside and methyl 2,3-anhydro-4,6-O-benzylidene-
α-D-mannopyranoside, respectively.
In contrast to many excellent ligands derived from monosaccharides, disaccharide chiral ligands have
been less studied.5 Recently, we reported a new preparative method of novel disaccharide phosphinites
∗
Corresponding authors. E-mail: uemura@scl.kyoto-u.ac.jp
0957-4166/99/$ - see front matter © 1999 Elsevier Science Ltd. All rights reserved.
PII: S0957-4166(99)00430-9

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from α,α-trehalose which functioned as chiral ligands for asymmetric Rh-catalyzed hydrogenation of
enamides to afford both enantiomers of amino acid derivatives.6 We also succeeded in a preparation
of water-soluble disaccharide phosphinite chiral ligands having polyhydroxy groups from α,α- and
β,β-trehaloses and their application to Rh-catalyzed hydrogenations of dehydroamino acids and their
esters in water.7 In this paper, we describe the synthesis of novel chiral disaccharide phosphine ligands
from α,α-trehalose in which phosphorus atoms are directly linked at 2,20-positions. These ligands are
expected to coordinate metals more effectively than phosphinite ligands, because the distances between
stereogenic centers of ligands and a metal center are shorter than those in the case of phosphinite
ligands. Furthermore, we tried to prepare 2,20-bisphosphine bearing polyhydroxy groups by the removal
of protecting groups. The hydroxy groups in the ligand usually play an important role in the transition
metal-catalyzed asymmetric reactions.8 For example, they can make the complex water-soluble, so that
phosphines bearing polyhydroxy groups deserve investigation.
2. Results and discussion
First, we prepared 4,6-O-benzylidene-2-(diphenylphosphino)-2-deoxy-α-D-altropyranosyl-(1,1)-4,6-
O-benzylidene-2-(diphenylphosphino)-2-deoxy-α-D-altropyranoside 1 from α,α-trehalose as shown in
Scheme 1.
Scheme 1. (a) Benzaldehyde dimenthyl acetal, P-TsOH·H2O, DMF, 100°C, 2 h, 91%; (b) mesyl chloride, pyridine, 0°C–rt, 24
h, 80%; (c) MeONa, acetone–MeOH, rt, 48 h, 61%; (d) PH2PNa, DMF, 50°C, 10 min, 70%; (e) 30% H2O2, CH2Cl2, 24 h, 98%
Protection of the 4,6:40,60-positions of α,α-trehalose with the benzylidene groups9 and the
mesylation of 2,3:20,30-positions followed by treatment with sodium methoxide gave 2,3-anhydro-
4,6-O-benzylidene-α-D-allopyranosyl-(1,1)-2,3-anhydro-4,6-O-benzylidene-α-D-allopyranoside 4.10
Although compound 4 was insoluble in most organic solvents, we succeeded in the preparation of the
compound 1 by treatment of 4 with Ph2PNa in DMF at 50°C. Oxidation of 1 with H2O2 gave rise to
diphosphine oxide 2.
Next, we tried to synthesize 2-(diphenylphosphino)-2-deoxy-α-D-altropyranosyl-(1,1)-2-
(diphenylphosphino)-2-deoxy-α-D-altropyranoside 5 as shown in Scheme 2. We attempted to
convert 1 into the corresponding phosphine 5 bearing polyhydroxy functionalities via deprotection of
benzylidene groups using: (i) acids, e.g. CH3COOH or conc. HCl; or (ii) catalytic and stoichiometric
palladium on carbon under hydrogen.11 However, all attempts to cleave the protecting groups failed,
probably due to the decomposition of product under acidic conditions before complete deprotection
of benzylidene groups and undesired complexation between phosphorus and palladium under

K. Yonehara et al. / Tetrahedron: Asymmetry 10 (1999) 4029–4035
4031
hydrogenolysis conditions. This was also the case when compound 2 was used as a starting material.
Although we succeeded in the deprotection of the benzylidene groups of 2 using conc. HCl, we could
not reduce the obtained phosphine oxide, 2-(diphenylphosphinooxyl)-2-deoxy-α-D-altropyranosyl-
(1,1)-2-(diphenylphosphinooxyl)-2-deoxy-α-D-altropyranoside 6, to 5 using trichlorosilane together
with triethylamine due to the insolubility of phosphine oxide under such reduction conditions.
Scheme 2. (a) 2,2-Dimenthoxypropane, p-TsOH·H2O, DMF, rt, 2 h, then Ac2O, pyridine, rt, 12 h, 60%; (b) K2CO3, MeOH,
rt, 1 h, 80%; (c) mesyl chloride, pyridine, 0°C–rt, 24 h, 81%; (d) MeONa, CH2Cl2, rt, 24 h, 58%; (e) Ph2PLi, THF,
−23°C, 30 min, 69%; (f) pyridinium p-toluenesulfonate (PPTS), MeOH:CH2Cl2=1:2, rt, 24 h, then Ac2O, pyridine, cat.
4-(dimethylamino)pyridine, rt 6 h, 38%; (g) K2CO3, MeOH, rt, 1 h, 60%
Thus, we replaced the benzylidene groups with isopropylidene ones in the 4,6:40,60-
positions because the latter are labile under acidic conditions by one order of magnitude
owing to steric and electronic effects.12 Protection of 4,6:4060-positions of α,α-trehalose
with isopropylidene groups,13 and the mesylation of 2,3:20,30-positions followed by treatment
with sodium methoxide gave 2,3-anhydro-4,6-O-isopropylidene-α-D-allopyranosyl-(1,1)-2,3-
anhydro-4,6-O-isopropylidene-α-D-allopyranoside 9. Compound 9 was easily converted into
2-(diphenylphosphino)-2-deoxy-4,6-O-isopropylidene-α-D-altropyranosyl-(1,1)-2-(diphenylphosphino)-
2-deoxy-4,6-O-isopropylidene-α-D-altropyranoside 10 using Ph2PLi in THF at −23°C. As expected,
the cleavage of isopropylidene groups of 10 occurred smoothly in the presence of pyridinium
p-toluenesulfonate (PPTS)14 in MeOH:CH2Cl2=1:2 at room temperature to give crude 2-(di-
phenylphosphino)-2-deoxy-α-D-altropyranosyl-(1,1)-2-(diphenylphosphino)-2-deoxy-α-D-altropyrano-
side 5. Acetylation of crude 5 with Ac2O/pyridine leading to 3,4,6-tri-O-acetyl-2-(diphenylphos-
phino)-2-deoxy-α-D-altropyranosyl-(1,1)-3,4,6-tri-O-acetyl-2-(diphenylphosphino)-2-deoxy-α-D-altro-
pyranoside 11 followed by deacetylation in the usual manner (K2CO3/MeOH) afforded pure 5.
In the 31P NMR of rhodium complex 12 prepared in situ from an equimolar amount of [Rh(cod)2]BF4
and 5 in CD3OD, a single resonance peak of a phosphorus nucleus was observed as a doublet: δ 41.6

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ppm (JRh–P=152.6 Hz). This result shows that the diphosphine 5 coordinates to rhodium in a bidentate
fashion.15 Unfortunately, neither the diphosphine 5 nor its rhodium complex 12 were appreciably
soluble in water, and we could not apply the complex to asymmetric hydrogenation of methyl α-
acetamidocinnamate in water.16
In summary, we prepared novel chiral disaccharide phosphines 1 and 10 from α,α-trehalose in which
the phosphorus atoms are directly linked at the 2,20-positions. We also succeeded in a deprotection of
the isopropylidene groups in 10 to give 5 bearing polyhydroxy groups, although it was only slightly
soluble in water. However, since the hydroxy group in the ligand can sometimes powerfully support the
stereodiscriminating ability of a metal catalyst,8 the ligand reported here may find application in the other
asymmetric reactions.
3. Experimental
3.1. General
Tetrahydrofuran (THF) was distilled from sodium benzophenone ketyl under argon. Dichloromethane,
triethylamine, and N,N-dimethylformamide (DMF) were distilled from calcium hydride. Methanol was
distilled from Mg(OMe)2. Analytical thin-layer chromatographies (TLC) were performed with silica
gel 60 Merck F-254 plates. Column chromatographies were performed with Merck silica gel 60. NMR
spectra were measured on JEOL EX-400, JEOL JNM-AL300, and JEOL JNM-GSX270 spectrometers
for solutions in CDCl3 or CD3OD with Me4Si as an internal standard (1H and 13C) or with P(OMe)3
as an external standard (31P). IR spectra were recorded with a Nicolet Impact 400 FT-IR spectrometer.
Optical rotations were measured on JASCO DIP-1000. Melting points are uncorrected. High-resolution
mass spectra (FAB HRMS) were obtained with a JEOL JMX-SX 102A spectrometer. α,α-Trehalose
dihydrate was purchased from Hayashibara Corporation.
3.2. 4,6-O-Benzylidene-2-(diphenylphosphino)-2-deoxy-α-D-altropyranosyl-(1,1)-4,6-O-benzylidene-
2-(diphenylphosphino)-2-deoxy-α-D-altropyranoside 1
To a stirred mixture of Ph2PH (0.52 mL, 3.0 mmol) and sodium hydride (0.068 g, 2.8 mmol) in dry
DMF (35 mL) was added the compound 4 (0.48 g, 1.0 mmol) in one portion under Ar and the mixture
was stirred for 10 min at 50°C. After the complete consumption of 4 was confirmed by TLC, NH4Cl
(0.16 g, 3.0 mmol) was added to the above solution, and the mixture was stirred for 30 min. The solvent
was removed under vacuum and the residue was subjected to column chromatography on SiO2 with
CHCl3:AcOEt (v/v=6:1) as an eluent to give the compound 1 (0.60 g, 0.70 mmol, 70%), as a white solid:
mp 128.0–130.0°C. [α]25 =+28.4 (c 0.5, CHCl3); 1H NMR (400 MHz, CDCl3) δ 3.23 (m, 2H), 3.71 (t,
D
J=9.8 Hz, 2H), 3.86 (m, 2H), 4.06–4.22 (m, 6H), 4.72 (d, J=5.4 Hz, 2H), 5.62 (s, 2H), 7.30–7.60 (m,
30H); 13C NMR (100 MHz, CDCl3) δ 44.8 (d, J=14.7 Hz), 59.3, 66.5 (d, J=18.3 Hz), 69.0, 77.4, 93.6 (d,
J=20.2 Hz), 102.2, 126.3, 128.2, 128.98, 129.0 (d, J=9.2 Hz), 129.1 (d, J=9.2 Hz), 129.7, 130.0, 133.0
(d, 20.2 Hz), 133.6 (d, J=20.2 Hz), 134.7 (d, J=12.8 Hz), 135.3 (d, J=14.7 Hz), 137.2; 31P NMR (161.9
MHz, CDCl3) δ −21.4; IR (KBr) 509 (w), 697 (s), 749 (s), 959 (s), 1006 (s), 1089 (s), 1121 (s), 1281
(w), 1380 (m), 1435 (m), 1724 (m), 1814 (w), 1893 (w), 1957 (w), 2860 (m), 2931 (m), 3069 (w), 3510
(m) cm−1; HRMS (FAB) calcd for C50H49O9P2 (M+H+): 855.2852. Found: 855.2816.

K. Yonehara et al. / Tetrahedron: Asymmetry 10 (1999) 4029–4035
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3.3. 4,6-O-Benzylidene-2-(diphenylphosphinooxyl)-2-deoxy-α-D-altropyranosyl-(1,1)-4,6-O-benzyl-
idene-2-(diphenylphosphinooxyl)-2-deoxy-α-D-altropyranoside 2
A 30% aqueous hydrogen peroxide (5 mL) was added at room temperature to the solution of the
compound 1 (0.85 g, 1.0 mmol) in CH2Cl2 (10 mL) and the mixture was stirred overnight. The solution
was washed with aqueous Na2S2O3 solution and the organic layer was dried over MgSO4. After the
solvent was removed under vacuum, the residue was subjected to column chromatography on SiO2 with
CH2Cl2:acetone (v/v=2:1) as an eluent to give the compound 2 (0.87 g, 0.98 mmol, 98%), as a white
solid: mp 201.3–202.0°C. [α]25=+28.9 (c 0.5, CHCl3); 1H NMR (400 MHz, CDCl3) δ 3.19 (d, J=11.2
D
Hz, 2H), 3.63–3.73 (m, 4H), 4.05–4.10 (m, 2H), 4.31–4.37 (m, 4H), 5.11 (d, J=8.3 Hz, 2H), 5.67 (s, 2H),
7.36–7.91 (m, 30 H); 13C NMR (100 MHz, CDCl3) δ 45.9 (d, J=66.2 Hz), 58.4, 64.6, 68.7, 76.5, 90.8,
102.0, 126.3–137.2 (8 carbons); 31P NMR (161.9 MHz, CDCl3) δ 25.0; IR (KBr) 554 (s), 699 (s), 753
(s), 870 (m), 974 (s), 1006(s), 1120 (s), 1188 (s), 1381 (w), 1438 (m), 1637 (w), 2866 (w), 3011 (w),
3059 (w), 3399 (m) cm−1; HRMS (FAB) calcd for C50H49O11P2 (M+H+): 887.2750. Found: 887.2720.
3.4. 4,6-O-Isopropylidene-2,3-di-O-mesyl-α-D-glucopyranosyl-(1,1)-4,6-O-isopropylidene-2,3-di-O-
mesyl-α-D-glucopyranoside 8
To a solution of the compound 7 (15.8 g, 37.4 mmol) in dry pyridine (200 mL) was slowly added
methanesulfonyl chloride (17 mL, 224 mmol) at 0°C. The solution was left standing at room temperature
overnight, then poured into ice-water, whereupon the product was precipitated. Filtration and recrystalli-
zation of crystalline compound from acetone–methanol gave the compound 8 (22.3 g, 30.4 mmol, 81%),
as a white solid: mp 152.1–153.3°C. [α]24=+88.2 (c 0.5, CHCl3); 1H NMR (270 MHz, CDCl3) δ 1.46
D
(s, 6H), 1.50 (s, 6H), 3.16 (s, 6H), 3.20 (s, 6H), 3.67 (m, 2H), 3.80 (t, J=9.6 Hz, 2H), 3.99–4.10 (m, 4H),
4.65 (dd, J=4.1, 9.6 Hz, 2H), 4.93 (t, J=9.6 Hz), 5.29 (d, J=4.1 Hz); 13C NMR (100 MHz, CDCl3) δ
19.4, 28.7, 38.9, 61.4, 64.0, 71.8, 75.7, 78.0, 95.2, 100.1; IR (KBr) 757 (m), 838 (s), 965 (s), 998 (m),
1040 (s), 1190 (s), 1362 (s), 1620 (w), 2943 (w), 2995 (w), 3024 (w), 3485 (m) cm−1; HRMS (FAB)
calcd for C22H39O19S4 (M+H+): 735.0968. Found: 735.0956.
3.5. 2,3-Anhydro-4,6-O-isopropylidene-α-D-allopyranosyl-(1,1)-2,3-anhydro-4,6-O-isopropylidene-α-
D-allopyranoside 9
To a solution of the compound 8 (10 g, 13.6 mmol) in dry CH2Cl2 (160 mL) was added 2 M sodium
methoxide–methanol solution (55 mL) and the mixture was stirred for 24 h. After the mixture was
diluted with CH2Cl2, the organic layer was washed with water and dried over MgSO4. The solvent
was removed under vacuum and the residue was subjected to column chromatography on SiO2 with
CHCl3:AcOEt (v/v=1:2) as an eluent to give the compound 9 (3.0 g, 7.9 mmol, 58%), as a white solid:
25
1
mp 197.6–198.1°C. [α] =+90.4 (c 0.5, CHCl3); H NMR (300 MHz, CDCl3) δ 1.44 (s, 6H), 1.51
D
(s, 6H), 3.40 (m, 2H), 3.45 (dd, J=2.8, 4.4 Hz, 2H), 3.62–3.70 (m, 2H), 3.79–3.84 (m, 2H), 3.99–4.03
(m, 4H), 5.28 (d, J=2.8 Hz); 13C NMR (100 MHz, CDCl3) δ 18.9, 28.9, 50.9, 53.0, 61.5, 62.2, 70.3,
89.7, 100.1; IR (KBr) 773 (m), 843 (m), 879 (s), 920 (s), 939 (s), 1004 (s), 1067 (s), 1107 (s), 1197 (s),
1268 (m), 1375 (m), 2892 (w), 2961 (w), 2995 (m) cm−1; HRMS (FAB) calcd for C18H27O9 (M+H+):
387.1655. Found: 387.1667.

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K. Yonehara et al. / Tetrahedron: Asymmetry 10 (1999) 4029–4035
3.6. 2-(Diphenylphosphino)-2-deoxy-4,6-O-isopropylidene-α-D-altropyranosyl-(1,1)-2-(diphenyl-
phosphino)-2-deoxy-4,6-O-isopropylidene-α-D-altropyranoside 10
A solution of the compound 9 (0.4 g, 1.0 mmol) in anhydrous THF (6 mL) was added dropwise under
N2 to a stirred solution of Ph2PLi (3.0 mmol) in anhydrous THF (4 mL) at −23°C. After the complete
consumption of 9 was confirmed by TLC, NH4Cl (0.16 g, 3.0 mmol) was added to the above solution, and
the mixture was stirred for 30 min. The solvent was removed under vacuum and the residue was subjected
to column chromatography on SiO2 with CHCl3:AcOEt (v/v=2:1) as an eluent to give the compound 10
(0.52 g, 0.69 mmol, 69%), as a white solid: mp 120.9–121.5°C. [α]25=+37.5 (c 0.5, CHCl3); 1H NMR
D
(400 MHz, CDCl3) δ 1.44 (s, 6H), 1.50 (s, 6H), 3.17 (m, 2H), 3.46 (dd, J=5.4, 10.3 Hz, 2H), 3.67 (t,
J=10.3 Hz, 2H), 3.87 (m, 2H), 3.99 (m, 2H), 4.11 (dd, J=2.9, 9.8 Hz, 2H), 4.68 (d, J=5.4 Hz, 2H),
7.35–7.58 (m, 20H); 13C NMR (100 MHz, CDCl3) δ 19.4, 29.2, 44.5 (d, J=14.7 Hz), 60.0, 62.3, 66.8
(d, J=16.6 Hz), 69.9, 93.7 (d, J=22.0 Hz), 100.0, 126.3, 128.3–129.9 (2 carbons), 133.0 (d, J=20.2 Hz),
133.5 (d, J=22.1 Hz), 133.5 (d, J=22.1 Hz), 135.1 (d, J=12.9 Hz), 135.4 (d, J=14.8 Hz); 31P NMR (161.9
MHz, CDCl3) δ −20.4; IR (KBr) 697 (s), 750 (s), 895 (m), 942 (s), 962 (s), 1002 (s), 1082 (s), 1121 (s),
1197 (s), 1269 (w), 1374 (m), 1382 (m), 1435 (s), 1481 (w), 2937 (m), 2992 (m), 3054 (m), 3435 (s)
cm−1; HRMS (FAB) calcd for C42H49O9P2 (M+H+): 759.2852. Found: 759.2842.
3.7. 3,4,6-Tri-O-acetyl-2-(diphenylphosphino)-2-deoxy-α-D-altropyranosyl-(1,1)-3,4,6-tri-O-acetyl-
2-(diphenylphosphino)-2-deoxy-α-D-altropyranoside 11
Pyridinium p-toluenesulfonate (0.9 g, 3.6 mmol) was added to a solution of the compound 10 (1.4
g, 1.8 mmol) in MeOH:CH2Cl2=1:2 (10 mL) and the mixture was stirred overnight. The solution was
neutralized by NaHCO3 (43 mg, 3.6 mmol) and the solvent was removed under vacuum. The residue
was subjected to column chromatography on SiO2 with CHCl3:CH3OH (v/v=10:1) as an eluent to give
the crude compound of 5. After the crude 5 was dissolved in CH2Cl2:Et3N=2:1 (7.5 mL), Ac2O (1.5
mL, 16 mmol) and a catalytic amount of 4-(dimethylamino)pyridine was added to this solution, and the
mixture was stirred at rt for 6 h. The mixture was diluted with CH2Cl2 and washed with aqueous NaHCO3
solution and dried over MgSO4. The solvent was removed under vacuum and the residue was subjected
to column chromatography on SiO2 with CHCl3:AcOEt (v/v=10:1) as an eluent to give the compound
11 (0.64 g, 0.69 mmol, 38%), as a white solid: mp 65.6–66.0°C. [α]25=+69.7 (c 0.5, CHCl3); 1H NMR
D
(400 MHz, CDCl3) δ 1.93 (s, 6H), 2.01 (s, 6H), 2.11 (s, 6H), 3.23 (d, J=2.4 Hz, 2H), 3.54 (dd, J=1.9,
11.3 Hz, 2H), 3.94 (m, 2H), 4.04 (dd, J=3.9, 11.3 Hz, 2H), 4.90 (d, J=6.84 Hz, 2H), 5.01 (m, 2H), 5.33
(dd, J=2.9, 9.8 Hz, 2H), 7.36–7.61 (m, 20H); 13C NMR (100 MHz, CDCl3) δ 20.7, 21.1, 41.6 (d, J=18.4
Hz), 65.1, 65.3, 65.4, 69.1 (d, J=20.2 Hz), 92.1 (d, J=22.1 Hz), 128.7 (d, J=7.4 Hz), 128.8 (d, J=7.3
Hz), 129.7, 130.0, 133.4 (d, J=7.9 Hz), 133.7 (d, J=7.3 Hz), 134.3 (d, J=12.9 Hz), 134.9 (d, J=14.7 Hz),
169.2, 170.1, 170.7; 31P NMR (161.9 MHz, CDCl3) δ −18.7; IR (KBr) 698 (s), 748 (m), 968 (s), 1036
(s), 1059 (m), 1129 (m), 1225 (s), 1372 (m), 1436 (m), 1482 (w), 1635 (w), 1744 (s), 1890 (w), 1972 (w),
2955 (w), 3056 (w) cm−1; HRMS (FAB) calcd for C48H53O15P2 (M+H+): 931.2859. Found: 931.2842.
3.8. 2-(Diphenylphosphino)-2-deoxy-α-D-altropyranosyl-(1,1)-2-(diphenylphosphino)-2-deoxy-α-D-
altropyranoside 5
To a solution of the compound 11 (0.36 g, 0.38 mmol) in CH3OH was added K2CO3 (26 mg, 0.19
mmol) under N2 and the mixture was stirred for 1 h. After the complete consumption of 11 was
confirmed by TLC, the solvent was removed under vacuum and the residue was subjected to column
chromatography on SiO2 with CHCl3:CH3OH(v/v=10:1) as an eluent to give the compound 5 (0.16 g,

K. Yonehara et al. / Tetrahedron: Asymmetry 10 (1999) 4029–4035
4035
25
1
0.23 mmol, 60%), as a white solid: mp 127.2–128.0°C. [α] =+45.0 (c 0.5, CH3OH); H NMR (400
D
MHz, CD3OD) δ 3.23 (m, 2H), 3.42 (dd, J=2.3, 12.0 Hz, 2H), 3.69 (dd, 3.7, 12.0 Hz, 2H), 3.77–3.84
(m, 4H), 4.09 (dd, J=3.3, 10.2 Hz, 2H), 4.75 (d, J=5.5 Hz, 2H), 7.36–7.59 (m, 20H); 13C NMR (100
MHz, CD3OD) δ 46.5 (d, J=14.5 Hz), 63.3, 66.7 (d, J=6.8 Hz), 70.7, 71.1, 95.8 (d, J=19.7 Hz), 129.9
(d, J=9.2 Hz), 130.0 (d, J=7.3 Hz), 130.7, 130.8, 134.4 (d, J=21.4 Hz), 134.7 (d, J=22.0 Hz), 137.1 (d,
J=16.6 Hz), 137.4 (d, J=12.9 Hz); 31P NMR (161.9 MHz, CD3OD) δ −21.6; IR (KBr) 697 (s), 742 (s),
960 (s), 1045 (s), 1065 (s), 1126 (s), 1435 (m), 1481 (w), 1636 (w), 2924 (m), 3071 (w), 3408 (s) cm−1;
HRMS (FAB) calcd for C36H41O9P2 (M+H+): 679.2226. Found: 679.2228.
3.9. Synthesis of rhodium complex 12
[Rh(cod)2]BF4 (12 mg, 3.0×10−2 mmol) and 5 (20 mg, 3.0×10−2 mmol) were dissolved in degassed
dry MeOH (1.0 mL) and the mixture was stirred under Ar. After 20 min, degassed dry Et2O (10 mL)
was added, and the complex precipitated. The supernatant solution was decanted, and degassed dry Et2O
(5.0 mL) was again added to the obtained solid. The product was separated by filtration, washed with
degassed dry Et2O (10 mL), and dried under vacuum to give 12 as an orange powder (14.6 mg, 1.5×10−2
mmol, 50%): mp (decomposition) 210.5–211.3°C; 31P NMR δ 41.6 ppm (JRh–P=152.6 Hz).
References
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15. At present we cannot rule out the possibility that the complex 12 contains a two phosphine ligands bridge between two
rhodium metal centers (Rh:ligand=2:2). The unambiguous structure of 12 has not yet been clarified.
16. Hydrogenation of methyl α-acetamidocinnamate in MeOH using the rhodium complex 12 gave the (S)-hydrogenated
product with 12% ee.