300
G. M. Mehltretter et al.
PAPER
Hewlett Packard HP 1090 liquid chromatograph equipped with a
DAD. Enantiomeric excess values were either determined by HPLC
of the isolated diol, or its bis-benzoate derivative. The retention
time of the major HPLC peak is printed in bold. The absolute con-
figurations of the products were either determined by comparison
with original samples or are based on the mnemonic device estab-
lished by Sharpless et al.18 The commercial bleach (13% available
chlorine) used was obtained from Fluka.
13C NMR: δ = 74.5, 33.3, 27.8, 22.7, 14.0.
MS (CI, isobutane): m/z (%) = 175 ([M + H]+, 2), 157 ([M – OH]+,
100), 139 (15), 117 (2), 97 (5), 87 (12), 86 (11), 83 (14), 69 (19).
3-Phenoxypropane-1,2-diol
HPLC (diol): Daicel Chiralcel OD-H, 20% i-PrOH in hexane, flow
rate 1.0 mL/min, tR = 6.7 (R), tR = 11.9 (S).
1H NMR (CDCl3): δ = 6.85–7.29 (m, 5 H), 3.99–4.12 (m, 3 H),
3.83, (dd, J = 3.7, 11.3 Hz, 1 H), 3.74 (dd, J = 5.2, 11.3 Hz, 1 H),
2.10 (br s, 2 H).
13C NMR: δ = 158.3, 129.6, 121.3, 114.5, 70.3, 69.1, 63.7.
MS (EI, 70 eV): m/z (%) = 168 ([M]+, 27), 119 (9), 94 (100), 77
Dihydroxylation of -Methylstyrene; 2-Phenylpropane-1,2-di-
ol; Typical Procedure
In a 100 mL Schlenk tube, K2[OsO2(OH)4] (2.95 mg, 8 µmol),
(DHQD)2PHAL (77.9 mg, 0.1 mmol), and K2CO3 (0.55 g, 4.0
mmol) were dissolved in a mixture of tert-BuOH (10 mL) and H2O
(10 mL), then a 13% bleach (1.3 mL, 3.0 mmol) was added. The bi-
phasic mixture was cooled to 0 °C in an ice-bath. Then α-methyl-
styrene (236 mg, 260 µL, 2.0 mmol) was added by a syringe in one
portion and the reaction mixture was stirred vigorously with a mag-
netic stirring bar. After 1 h, Na2SO3 (500 mg) was added and the
mixture was warmed to r.t. under stirring. The mixture was then ex-
tracted with EtOAc (20 mL). The organic layer was dried (MgSO4)
and submitted for GC analysis after addition of diethyleneglycol
dibutyl ether (100 µL) as an internal GC standard. For isolation of
the product, the solvent was removed under reduced pressure and
the crude diol purified by column chromatography (hexane–EtOAc,
2:1) to give 2-phenylpropane-1,2-diol (301 mg, 99%) as a white sol-
id. HPLC analysis of the pure 1,2-diol showed an enantiomeric ex-
cess of 91%.
(17).
3-(Trimethylsilyl)propane-1,2-diol
HPLC (bis-benzoate): Daicel Chiralcel OD-H, 0.2% EtOH in hex-
ane, flow rate 1.0 mL/min, tR = 9.3 (S), tR = 10.5 (R).
1H NMR (CDCl3): δ = 3.68–3.86 (m, 2 H), 3.40–3.58 (m, 2 H), 3.28
(dd, J = 11.0, 8.4 Hz, 1 H), 0.76 (dd, J = 14.5, 8.1 Hz, 1 H), 0.65
(dd, J = 14.5, 4.4 Hz, 1 H), 0.01 (s, 9 H).
13C NMR: δ = 70.3, 68.9, 21.5, –0.9.
MS (CI, isobutane): m/z (%) = 149 ([M + H]+, 1), 131 ([M – OH]+,
77), 115 (11), 91 (15), 75 {[M – Si(CH3)3)]+, 100}, 73 (21).
3-(3,4-Dimethoxyphenyl)propane-1,2-diol
1H NMR (CDCl3): δ = 6.8 (d, J = 8.13 Hz, 1 H), 6.73–6.75 (m, 2 H),
3.87–3.95 (m, 1 H), 3.86 (s, 3 H), 3.84 (s, 3 H), 3.66–3,71 (m, 1 H),
3.51 (m, 1 H), 2.74 (dd, J = 13.78, 5.17 Hz, 1 H), 2.67 (dd,
J = 13.78, 8.13 Hz, 1 H), 2.06 (d, J = 3.44 Hz, 1 H), 1.94 (m, 1 H).
HPLC (diol): (R,R)-Whelk-O1, 2% EtOH in hexane, flow rate 1.0
mL/min, tR = 14.4 (S), 16.7 (R).
1H NMR (CDCl3): δ = 7.23–7.41 (m, 5 H), 3.74 (d, J = 11.1 Hz, 1
H), 3.58 (d, J = 11.1 Hz, 1 H), 2.39 (br s, 2 H), 1.50 (s, 3 H).
13C NMR: δ = 148.9, 147.7, 130.2, 121.2, 112.4, 111.3, 73, 66, 55.9,
55.8, 39.3.
13C NMR: δ = 144.9, 128.4, 127.1, 125.0, 74.8, 71.0, 26.0.
MS (EI, 70 eV): m/z = 212 ([M]+, 31), 152 (22), 151 (100), 137 (18).
MS (EI, 70 eV): m/z (%) = 152 ([M]+, 2), 135 (2), 121 (88), 105 (5),
91 (6), 77 (10), 51 (5), 43 (100), 31 (3).
HPLC (diol): Daicel Chiralcel OF-117, 17.4% i-PrOH in hexane,
flow rate 2.0 mL/min, tR = 9.6 (R), tR = 11.4 (S).
1-Phenylethane-1,2-diol
HPLC (diol): Daicel Chiralcel OB-H, 5% i-PrOH in hexane, flow
rate 1.0 mL/min, tR = 12.5 (R), 16.2 (S).
1H NMR (CDCl3): δ = 7.28–7.34 (m, 5 H), 4.79 (dd, J = 3.6, 8.2 Hz,
1 H), 3.72 (dd, J = 3.6, 11.4 Hz, 1 H), 3.63 (dd, J = 8.2, 11.4 Hz, 1
H), 2.6 (s, 2 H).
13C NMR: δ = 140.4, 128.5, 128.0, 126.0, 74.7, 68.0.
MS (EI, 70 eV): m/z (%) = 138 ([M]+, 9), 121 (14), 107 (100), 79
Acknowledgments
The authors thank Mrs. I. Stahr for excellent technical support, and
Dr. C. Fischer for her continuous help with the HPLC analysis. We
also thank Prof. B. Lücke and Dr. A. Köckritz (both ACA, Berlin)
for a fruitful cooperation. Financial support of the dihydroxylation
project from the Bundesministerium für Bildung und Forschung
(BMBF), Bayer AG, the Ministry of Education, Science and Cul-
tural Affairs of Mecklenburg-Vorpommern, and the ‘Fonds der
Chemischen Industrie’ is gratefully acknowledged.
(56), 77 (29), 51 (6), 31 (4).
1-Phenylcyclohexane-1,2-diol
HPLC (diol): Whelk (25 cm × 0.46 cm i.d.), 10% i-PrOH in hexane,
flow rate 1.0 mL/min, tR = 4.4 (S,S), tR = 6.4 (R,R).
1H NMR (CDCl3): δ = 7.21–7.53 (m, 5 H), 3.96 (dd, J = 4.7, 11.1
References
(1) Worldwide production capacities for ethylene glycol in
1995: 9.7 Mio to/a; worldwide production of 1,2-propylene
glycol in 1994: 1.1 Mio to/a: (a) Weissermel, K.; Arpe, H.-
J. Industrielle Organische Chemie; Wiley-VCH: Weinheim,
1998, 5th ed., 167. (b) Weissermel, K.; Arpe, H.-J.
Industrielle Organische Chemie; Wiley-VCH: Weinheim,
1998, 5th ed., 302.
Hz, 1 H), 1.35–1.89 (m, 11 H).
13C NMR: δ = 146.3, 128.5, 127.0, 125.1, 75.7, 74.5, 38.5, 30.9,
24.3, 21.1.
MS (EI, 70 eV): m/z (%) = 192 ([M]+, 59), 174 (20), 145 (10), 133
(100), 120 (36), 107 (5), 105 (68), 91 (18), 77 (36), 55 (26).
(2) (a) Szmant, H. H. Organic Building Blocks of the Chemical
Industry; Wiley: New York, 1989, 347. (b)Pohl, G.; Gaube,
H. In Ullmann’s Encyclopedia of Industrial Chemistry, Vol.
A1; VCH: Weinheim, 1985, 305–320.
Decane-5,6-diol
HPLC (bis-benzoate): Daicel Chiralcel OD-H, 0.2% i-PrOH in hex-
ane, flow rate 1.0 mL/min, tR = 6.0 (S,S), tR = 7.3 (R,R).
1H NMR (CDCl3): δ = 3.37–3.39 (m, 2 H), 2.12 (s, 2 H), 1.28–1.50
(m, 12 H), 0.89 (t, J = 7.2 Hz, 6 H).
Synthesis 2003, No. 2, 295–301 ISSN 0039-7881 © Thieme Stuttgart · New York