optimal chiral cooperativity that induces the highest enantio-
selectivity.
3,5-Bis{[(S
)-1,10-binaphthyl-2,20-diyl]phosphite}-6-deoxy-1,2-
O-isopropylidene-a-D-glucofuranose (6). Treatment of in situ
formed phosphorochloridite (2.2 mmol) and 15 (0.21 g, 1
mmol) as described for compound 5 afforded diphosphite 6,
which was purified by flash chromatography (eluent: toluene;
Rf 0.45) to produce 0.42 g (51%) of a white powder. Anal.
Calcd. for C49H38O9P2: C, 70.67; H, 4.60. Found: C, 70.88;
H, 4.98. 31P NMR, d: 146.8 (d, 1P, 6JP–P ¼ 12.1 Hz), 151.0 (d, 1P,
Experimental
Materials and methods
1
6JP–P ¼ 12.1 Hz). H NMR, d: 1.11 (s, 3H, CH3), 1.41 (s, 3H,
All experiments were carried out under argon atmosphere.
All solvents were dried using standard methods and distilled
prior to use. Compounds 154d and 164d and ligands 1112 and
1212 were prepared by previously described methods. Phos-
phorochloridites were prepared in analogy with literature
procedures.4b
3
CH3), 1.45 (d, 3H, H-6, J6–5 ¼ 6.0 Hz), 4.02 (dd, 1H, H-4,
3
3
3J4–5 ¼ 8.8 Hz, J4–3 ¼ 2.4 Hz), 4.31 (d, 1H, H-2, J2–1 ¼ 3.2
3
Hz), 4.77 (m, 1H, H-5), 4.92 (dd, 1H, H-3, J3–4 ¼ 2.4 Hz,
3J3–P ¼ 7.6 Hz), 5.73 (d, 1H, H-1, J1–2 ¼ 3.2 Hz), 7.1–8.0 (m,
3
24H, CH=). 13C NMR, d: 21.2 (d, C-6, JC–P ¼ 3.8 Hz), 26.2
(CH3), 26.8 (CH3), 69.3 (d, C-5, JC–P ¼ 16.6 Hz), 77.8 (m, C-3),
82.8 (t, C-4, JC–P ¼ 7.6 Hz), 84.3 (C-2), 105.0 (C-1), 112.3
(CMe2), 121.8 (CH=), 121.9 (CH=), 122.0 (CH=), 122.1 (CH=),
125.0 (CH=), 125.2 (CH=), 125.3 (CH=), 125.4 (CH=), 126.3
(CH=), 126.4 (CH=), 126.6 (CH=), 127.1 (CH=), 127.2 (CH=),
127.3 (CH=), 128.4 (CH=), 128.5 (CH=), 128.6 (CH=), 129.2
(CH=), 130.0 (CH=), 130.2 (CH=), 130.4 (CH=), 130.5 (CH=),
130.8 (CH=), 132.8 (C), 132.9 (C), 133.1 (C), 147.6 (C), 148.2
(C), 148.3 (C), 148.4 (C).
Elemental analyses were performed on a Carlo Erba EA-
1108 instrument. 1H, 13C{1H} and 31P{1H} NMR spectra were
recorded on a Varian Gemini 400 MHz spectrometer. Che-
mical shifts were relative to SiMe4 (1H and 13C) as internal
standard or H3PO4 (31P) as external standard. All assignments
in NMR spectra were determined by COSY and HETCOR
spectra. Gas chromatographic analyses were run on a Hewlett–
Packard HP 5890A instrument (split=splitless injector, J&W
Scientific, Ultra-2 25 m column, internal diameter 0.2 mm, film
thickness 0.33 mm, carrier gas: 150 kPa He, F.I.D. detector)
equipped with a Hewlett–Packard HP 3396 series II integrator.
Hydroformylation reactions were carried out in a home-
made 100 mL stainless steel autoclave. Enantiomeric excesses
were measured after oxidation of the aldehydes to the cor-
responding carboxylic acids on a Hewlett–Packard HP 5890A
gas chromatograph (split=splitless injector, J&W Scientific,
FS-Cyclodex b-I=P 50 m column, internal diameter 0.2 mm,
film thickness 0.33 mm, carrier gas: 100 kPa He, F.I.D.
detector). Absolute configuration was determined by compar-
ing the retention times with optically pure (S)-(þ)-2-phenyl-
propionic and (R)-(ꢁ)-2-phenylpropionic acids.
3,5-Bis{[(R)-3,30-bistrimethylsilyl-1,10-binaphthyl-2,20-diyl]-
phosphite}-6-deoxy-1,2-O-isopropylidene-a-D-glucofuranose
(7). Treatment of in situ formed phosphorochloridite (2.2
mmol) and 15 (0.21 g, 1 mmol) as described for compound 5
afforded diphosphite 7, which was purified by flash chromato-
graphy (eluent: toluene; Rf 0.50). Yield: 0.41 g (36%) of a
white powder. Anal. Calcd. for C61H70O9P2Si4: C, 65.33; H,
6.29. Found: C, 65.51; H, 6.43. 31P NMR, d: 145.3 (s), 148.7
1
(s). H NMR, d: 0.32 (s, 9H, CH3–Si), 0.34 (s, 9H, CH3–Si),
0.35 (s, 9H, CH3–Si), 0.40 (s, 9H, CH3–Si), 0.84 (s, 3H, CH3),
3
1.11 (d, 3H, H-6, J6–5 ¼ 8.0 Hz), 1.25 (s, 3H, CH3), 4.07
(dd, 1H, H-4, 3J4–5 ¼ 3.2 Hz, 3J4–3 ¼ 2.8 Hz), 4.15 (d, 1H, H-2,
3
3
3J2–1 ¼ 3.2 Hz), 4.24 (dd, 1H, H-3, J3–P ¼ 8.8 Hz, J4–3 ¼ 2.8
Syntheses
3
Hz), 4.36 (m, 1H, H-5), 5.70 (d, 1H, H-1, J1–2 ¼ 3.2 Hz), 7.0–
7.4 (m, 12H, CH=), 7.8–8.1 (m, 8H, CH=). 13C NMR, d: ꢁ0.9
(CH3–Si), ꢁ0.1 (CH3–Si), 0.1 (CH3–Si), 0.2 (CH3–Si), 18.5 (C-
6), 25.4 (CH3), 29.7 (CH3), 71.0 (d, C-5, JC–P ¼ 6.4 Hz), 78.5
(C-3), 82.5 (b, C-4), 83.3 (m, C-2), 104.4 (C-1), 111.4 (CMe2),
123.6 (CH=), 123.9 (CH=), 124.5 (CH=), 124.8 (CH=), 126.1
(CH=), 126.5 (CH=), 126.6 (CH=), 126.8 (CH=), 127.5 (CH=),
128.1 (CH=), 128.3 (CH=), 128.4 (CH=), 129.2 (CH=), 130.5
(C), 130.6 (C), 130.8 (C), 130.9 (C), 132.3 (C), 132.4 (C), 133.5
(C), 133.6 (C), 133.8 (C), 134.2 (C), 136.3 (CH=), 136.7 (CH=),
137.0 (CH=), 151.1 (C), 151.3 (C).
3,5-Bis{[(R)-1,10-binaphthyl-2,20-diyl]phosphite}-6-deoxy-1,2-
O-isopropylidene-a-D-glucofuranose (5). Following a standard
procedure,4d in situ formed phosphorochloridite (2.2 mmol)
was dissolved in toluene (5 mL) to which pyridine (0.36 mL,
4.6 mmol) was added. 6-Desoxy-1,2-O-isopropylidene-a-D-
glucofuranose 15 (0.21 g, 1 mmol) was azeotropically dried
with toluene (3 ꢂ 1 mL) and dissolved in toluene (10 mL),
to which pyridine (0.18 mL, 2.3 mmol) had been added. The
diol solution was slowly transferred over 30 min to the solu-
tion of phosphorochloridite at room temperature. The reac-
tion mixture was stirred overnight at reflux and the pyridine
salts were removed by filtration. Evaporation of the solvent
gave a white foam, which was purified by flash chromato-
graphy (eluent: toluene; Rf 0.45) to produce 0.45 g (55%)
of a white powder. Anal. Calcd. for C49H38O9P2: C, 70.67; H,
4.60. Found: C, 70.74; H, 4.71. 31P NMR, d: 149.6 (d, 1P,
3,5-Bis{[(S)-3,30-bistrimethylsilyl-1,10-binaphthyl-2,20-diyl]-
phosphite}-6-deoxy-1,2-O-isopropylidene-a-D-glucofuranose
(8). Treatment of in situ formed phosphorochloridite (2.2
mmol) and 15 (0.21 g, 1 mmol) as described for compound 5
afforded diphosphite 8, which was purified by flash chroma-
tography (eluent: toluene; Rf 0.50). Yield: 0.37 g (34%) of a
white powder. Anal. Calcd. for C61H70O9P2Si4: C, 65.33; H,
6.29. Found: C, 65.61; H, 6.33. 31P NMR, d: 147.2 (d, 1P,
6
6JP–P ¼ 34.2 Hz), 153.1 (d, 1P, JP–P ¼ 34.2 Hz). 1H NMR,
3
d: 1.28 (s, 3H, CH3), 1.42 (s, 3H, CH3), 1.47 (d, 3H, H-6, J6–
3
3
¼ 6.0 Hz), 4.09 (dd, 1H, H-4, J4–5 ¼ 8.8 Hz, J4–3 ¼ 2.4 Hz),
5
3
6
1
6JP–P ¼ 31.6 Hz), 147.5 (d, 1P, JP–P ¼ 31.6 Hz). H NMR, d:
4.70 (m, 1H, H-5), 4.74 (d, 1H, H-2, J2–1 ¼ 3.6 Hz), 4.95 (dd,
1H, H-3, 3J3–4 ¼ 2.4 Hz, 3J3-P ¼ 8.8 Hz), 5.86 (d, 1H, H-1, 3J1–
0.25 (s, 9H, CH3–Si), 0.26 (s, 9H, CH3–Si), 0.28 (s, 9H, CH3–
¼ 3.6 Hz), 7.1–8.0 (m, 24H, CH=). 13C NMR, d: 20.9 (d, C-6,
3
Si), 0.33 (s, 9H, CH3–Si), 0.73 (d, 3H, H-6, J6–5 ¼ 6.4 Hz),
2
JC–P ¼ 3.2 Hz), 26.3 (CH3), 26.7 (CH3), 68.8 (d, C-5, JC–P
¼
1.03 (s, 3H, CH3), 1.11 (s, 3H, CH3), 2.54 (d, 1H, H-2,
3
3J2–1 ¼ 3.6), 3.69 (dd, 1H, H-4, J4–5 ¼ 9.0 Hz, 3J4–3 ¼ 2.7 Hz),
21.2 Hz), 77.1 (m, C-3), 82.8 (t, C-4, JC–P ¼ 7.3 Hz), 84.2 (d,
C-2, JC–P ¼ 3.4 Hz), 104.9 (C-1), 112.3 (CMe2), 121.1 (CH=),
121.7 (CH=), 124.8 (CH=), 124.9 (CH=), 125.0 (CH=), 125.2
(CH=), 126.1 (CH=), 126.2 (CH=), 126.3 (CH=), 127.0 (CH=),
127.1 (CH=), 128.2 (CH=), 128.3 (CH=), 129.0 (CH=), 129.8
(CH=), 130.1 (CH=), 130.3 (CH=), 130.5 (CH=), 131.4 (C),
131.7 (C), 131.8 (C), 132.9 (C), 133.0 (C), 146.9 (C), 147.1 (C),
147.4 (C).
4.46 (m, 1H, H-5), 4.57 (m, 1H, H-3), 4.99 (d, 1H, H-1, 3J1–2
¼
3.6 Hz), 6.9–7.3 (m, 12H, CH=), 7.7–7.9 (m, 8H, CH=). 13C
NMR, d: 0.3 (CH3–Si), 20.0 (C-6), 26.2 (CH3), 29.7 (CH3),
68.0 (C-5), 77.4 (m, C-3), 82.5 (m, C-4), 83.5 (C-2), 104.6 (C-1),
111.0 (CMe2), 124.4 (CH=), 124.6 (CH=), 124.8 (CH=), 125.0
(CH=), 126.1 (CH=), 126.3 (CH=), 126.5 (CH=), 126.7 (CH=),
128.2 (CH=), 128.4 (CH=), 129.0 (CH=), 130.4 (C), 130.5 (C),
New J. Chem., 2002, 26, 827–833
831