C. D o¨ bler et al. / Journal of Organometallic Chemistry 621 (2001) 70–76
75
1
3
1
00.6 MHz). Chemical shifts (l) are given in ppm and
3.74 (d, J=11.1 Hz, 1H), 7.23–7.41 (m, 5H). C-NMR:
l=26.0, 71.0, 74.8, 125.0, 127.1, 128.4, 144.9. MS (EI,
refer to residual solvent as an internal standard. Gas
chromatography was performed on a Hewlett Packard
HP 6890 chromatograph with a HP5 column. Mass
spectra were recorded on a AMD 402/3 mass spectro-
meter. The products were purified on silica gel 60,
+
70 eV), m/e: 152 ([M] , 2), 135 (2), 121 (88), 105 (5), 91
(6), 77 (10), 51 (5), 43 (100), 31 (3). HPLC (diol):
(R,R)-Whelk-O1, 2% EtOH in hexane, flow rate 1.0 ml
min , t
1,2-Octanediol: H-NMR (CDCl ): l=0.85 (t, J=6.8
3
Hz, 3H), 1.21–1.29 (m, 10H), 2.25 (brs, 2H), 3.37 (dd,
J=7.7, 11.1 Hz, 1H), 3.50 (dd, J=2.8, 11.1 Hz, 1H),
.59–3.65 (m, 1H). C-NMR: l=14.0, 22.6, 25.5, 29.3,
1.7, 33.1, 66.7, 72.4. MS (EI, 70 eV), m/e: 129 ([M] ),
−
1
=14.4 (S), 16.7 (R).
R
1
2
30-400 mesh (Merck). High-performance liquid chro-
matography was carried out using a Hewlett Packard HP
090 liquid chromatograph equipped with a DAD.
1
13
3
3
Enantiomeric excess values were either determined by
HPLC of the isolated diol or its bisbenzoate derivative.
+
1
15, 97, 55. HPLC (bisbenzoate): (R,R)-Whelk-O1, 0.5%
PrOH in hexane, flow rate 1.0 ml min , t =13.6 (R),
(
The retention time of the major HPLC peak is printed
i
−1
in bold.) The absolute configurations of the products
were either determined by comparison with original
samples or are based on the mnemonic device established
by Sharpless et al. [21].
General procedure for the dihydroxylation: In a 200
ml steel autoclave (Roth GmbH) equipped with a mag-
netic stirrer and a glass inline, K [OsO (OH) ] (either as
R
tR=15.8 (S).
1
1
-Phenyl-1,2-ethanediol: H-NMR (CDCl ): l=2.6
3
s, 2H), 3.63 (dd, J=8.2, 11.4 Hz, 1H), 3.72 (dd, J=3.6,
1.4 Hz), 4.79 (dd, J=3.6, 8.2 Hz, 1H), 7.28–7.34 (m,
H). C-NMR: l=68.0, 74.7, 126.0, 128.0, 128.5, 140.4.
MS (EI, 70 eV), m/e: 138 ([M] , 9), 121 (14), 107 (100),
79 (56), 77 (29), 51 (6), 31 (4). HPLC (diol): Daicel
Chiralcel OB-H, 5% PrOH in hexane, flow rate 1.0 ml
(
1
5
13
+
2
2
4
−
1
a solid or in the form of a freshly prepared 2 mmol l
i
solution in aqueous phosphate buffer) and the ligand
were dissolved in a mixture of 25 ml aqueous buffer
solution and 10 ml tert-BuOH. To this was added 2 mmol
olefin and the autoclave was closed, pressurized with air
and heated to 50°C. After 9–24 h the reaction mixture
was cooled to room temperature whilst stirring. A small
amount of Na SO was added, the mixture was then
−
1
min , t =12.5 (R), 16.2 (S).
R
1
1
-Phenyl-1,2-cyclohexanediol:
H-NMR (CDCl3):
l=1.35–1.89 (m, 11H), 3.96 (dd, J=4.7, 11.1 Hz, 1H),
.21–7.53 (m, 5H). C-NMR: l=21.1, 24.3, 30.9, 38.5,
4.5, 75.7, 125.1, 127.0, 128.5, 146.3; MS (EI, 70 eV),
m/e: 192 ([M] , 59), 174 (20), 145 (10), 133 (100), 120
36), 107 (5), 105 (68), 91 (18), 77 (36), 55 (26). HPLC
diol): Whelk (25 cm×0.46 cm I.D.), 10% PrOH in
hexane, flow rate 1.0 ml min , t =4.4 (S, S), t =6.4
R, R).
,2-Diphenyl-1,2-ethanediol: H-NMR (CDCl ): l=
.73 (brs, 2H), 4.69 (s, 2H), 7.09–7.22 (m, 10H). C-
NMR: l=79.1, 126.9, 127.9, 128.1, 139.8. MS (EI, 70
eV), m/e: 214 ([M] , 1), 197 (14), 108 (100), 107 (89), 79
13
7
7
+
2
3
(
(
extracted with 2×20 ml of ethyl acetate. The combined
organic layers were dried over MgSO and submitted
i
4
−1
R
R
for GC analysis after addition of 100 ml of diethylene-
glycol di-n-butyl ether as an internal GC standard.
Procedure for the dihydroxylation (10 mmol scale): 10
mmol a-methylstyrene or 1-octene was reacted with 3.7
mg (0.01 mmol) K [OsO (OH) ] and 46.1 mg (0.06 mmol)
(
1
1
3
13
2
2
2
4
+
(DHQD) PHAL in 50 ml buffer solution and 20 ml
2
(
78), 77 (40), 51 (11). HPLC (diol): Daicel Chiralcel
OB-H, 10% EtOH in hexane, flow rate 1.0 ml min
tert-BuOH as described above.
−1
,
After 24 h Na SO was added and the mixture was
2
3
t =8.0 (R, R), 10.1 (S, S).
R
extracted with 2×30 ml of ethyl acetate. The combined
organic layers were dried over MgSO , the solvent was
removed under reduced pressure and the crude diol
purified by column chromatography.
1
5
,6-Decanediol: H-NMR (CDCl ): l=0.89 (t, J=7.2
Hz, 6H), 1.28–1.50 (m, 12H), 2.12 (s, 2H), 3.37–3.39 (m,
H). C-NMR: l=14.0, 22.7, 27.8, 33.3, 74.5. MS (CI,
3
4
13
2
+
+
isobutane), m/e: 175 ([M+H] , 2), 157 ([M−OH] ,
00), 139 (15), 117 (2), 97 (5), 87 (12), 86 (11), 83 (14),
69 (19). HPLC (bisbenzoate): Daicel Chiralcel OD-H,
(
R)-2-Phenyl-1,2-propanediol: Oil, 1.43 g (94% yield),
1
2
0
ee 78% (HPLC), [h] −8.8 (c 1.76, CHCl ). Lit. [22]:
D
3
2
D
5
[
h] −10.6 (c 1.76, CHCl , ee 95%). Anal. Calc. for
i
−1
3
0.2% PrOH in hexane, flow rate 1.0 ml min , t =6.0
R
C H O (152.2): C, 71.02; H, 7.95. Found: C, 70.82; H,
7
9
12
2
(S, S), t =7.3 (R, R).
3
R
1
.84%.
-Phenoxy-1,2-propanediol: H-NMR (CDCl ): l=
.10 (brs, 2H), 3.74 (dd, J=5.2, 11.3 Hz, 1H), 3.83, (dd,
J=3.7, 11.3 Hz, 1H), 3.99–4.12 (m, 3H), 6.85–7.29 (m,
5H). C-NMR: l=63.7, 69.1, 70.3, 114.5, 121.3, 129.6,
3
(
R)-1,2-Octanediol: Oil, 1.39 g (95% yield), ee 61%
2
2
0
(
HPLC, bisbenzoate), [h] 9.6 (c 1.15, EtOH). Lit.. [23]:
D
2
D
5
13
[
h] 15.6 (c 1.15, EtOH). Anal. Calc. for C H O2
8
18
+
(
146.5): C, 65.69; H, 12.41. Found: C, 65.39; H, 12.18%.
158.3. MS (EI, 70 eV), m/e: 168 ([M] , 27), 119 (9), 94
(
100), 77 (17). HPLC (diol): Daicel Chiralcel OD-H, 20%
i
−1
PrOH in hexane, flow rate 1.0 ml min , t =6.7 (R),
R
4
. Physical data for diols
tR=11.9 (S).
1
1
H,1H,2H-Perfluorooctane-1,2-diol: H-NMR (D6-
1
2-Phenyl-1,2-propanediol: H-NMR (CDCl ): l=
DMSO): l=3.74 (m, 1H), 3.93 (m, 1H), 4.30 (m, 1H),
5.24 (s, 1H), 6.49 (s, 1H). C-NMR: l=60.2, 76.9,
3
13
1
.50 (s, 3H), 2.39 (brs, 2H), 3.58 (d, J=11.1 Hz, 1H),