Sodium Chlorite in Asymmetric Dihydroxylation
reaction mixture was determined simultaneously with the
withdrawal of the aliquot. The total reaction time was 30 min.
mM diphenyl ether acetonitrile/water (7:3) solution. Samples
were analyzed with HPLC.
Dih yd r oxyla tion of Styr en e in th e P r esen ce of K
CN) ] a n d GC Sta n d a r d in Non bu ffer ed Con d ition s. A
50 mL three-necked flask equipped with a magnetic stirring
3
[F e-
Gen er a l P r oced u r e for Asym m etr ic Dih yd r oxyla tion .
A 250 mL three-necked flask equipped with a magnetic stirring
bar and a pH electrode was charged with 10 mmol of olefin,
(
2
6
bar and a pH electrode was charged with 9.88 g (30 mmol) of
[Fe(CN) ], 78 mg (0.1 mmol) of ligand ((DHQD) PHAL), 14.7
mg (0.04 mmol) of K OsO ‚2H O, 0.78 g of menthol (5.0 mmol,
internal GC standard), and 100 mL of H
5.5 g of NaCl, 78 mg (0.1 mmol) of ligand ((DHQD)
14.7 mg (0.04 mmol) of K OsO ‚2H O, and 100 mL of H
BuOH (1:1) solution (or 100 mL of H O/methyl ethyl ketone
2
PHAL),
K
3
6
2
2
4
2
2
O/
t
2
4
2
2
t
O/ BuOH (1:1)
(1:1) solution, Table 1, entry 8). The biphasic mixture was
cooled in an ice/water bath to 0-1 °C. To the mixture was
2
added 0.1 mL of 1 M NaClO solution via syringe. pH was
2
solution. pH was adjusted to 11.5 with 0.5 M NaOH. Reaction
was initiated by adding 10 mmol of styrene to the reaction
mixture in one portion. A 0.1 mL aliquot was withdrawn from
the reaction mixture after 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0,
adjusted to about 11.8 with 0.5 M NaOH. In total, 5.0 mL (5
mmol) of 1 M NaClO solution was added portionwise after
2
VI
4
.5, 5.0, 5.5, 6.0, and 30 min. Samples were diluted with 0.5
the pale violet color of Os appeared in the water layer or the
pH dropped to the same level as before the addition of the
oxidant. The reaction mixture was transferred to a separatory
funnel, and 100 mL of EtOAc was added. The organic layer
was extracted with 50 mL of 1 M HCl, 50 mL of saturated
mL of EtOAc, and the resulting organic layer was analyzed
using GC. The pH of the reaction mixture was determined
simultaneously with the withdrawal of the aliquot.
Dih yd r oxyla tion of Styr en e: Rea ction Ra te P r ofile of
th e Na ClO
2
Dih yd r oxyla tion (F igu r e 2). A 250 mL three-
Na
Na
2
CO
SO
3
, and 50 mL of brine. The organic layer was dried with
, filtered, and evaporated in a rotary evaporator.
necked flask equipped with a magnetic stirring bar and a pH
electrode was charged with 5.5 g of NaCl, 78 mg (0.1 mmol) of
2
4
1-P h en yleth a n e-1,2-d iol. The crude product was purified
ligand ((DHQD)
8
1
2
PHAL), 14.7 mg (0.04 mmol) of K
5 mg (0.75 mmol) of NaClO , and 100 mL of H
) solution. pH was adjusted to 11.8 with 0.5 M NaOH. The
2
OsO
O/ BuOH (1:
4
‚2H
2
O,
by flash chromatography using a 2:1 solution of EtOAc/n-
t
hexane as the eluent: yield 1.01 g (73%); mp 64-65 °C (lit.10a
2
2
1
66-67 °C); H NMR (200 MHz, d-acetone) δ 7.30 (m, 5H), 4.72
biphasic mixture was cooled in an ice/water bath to 0-1 °C.
Reaction was initiated by adding 1 mmol of styrene to the
reaction mixture in one portion. A 100 µL aliquot was
withdrawn from the reaction mixture after 20, 40, 60, 90, 120,
(ddd, J ) 4, 4, 4 Hz, 1H), 4.32 (d, J ) 4 Hz, 1H), 3.82 (dd, J )
7, 6 Hz, 1H), 3.57 (m, 2H); HRMS m/z (M +Na) found 161.0570,
8 10 2
calcd 161.0578 (C H O Na).
1,2-Dip h en yleth a n e-1,2-d iol. The crude product was puri-
1
80, 240, 300, 360, and 480 s. The samples were then diluted
fied by recrystallization from toluene: yield 1.35 g (63%); mp
139-140 °C (lit.1 139-140 °C); H NMR (200 MHz, d-acetone)
0b
1
with 2 mL of 0.5 mM diphenyl ether acetonitrile/water (7:3)
solution. Samples were analyzed with HPLC.
δ 7.17 (br, 10H), 4.62 (br, 4H); HRMS m/z (M + Na) found
2
37.0869, calcd 237.0891 (C14
14 2
H O Na).
Dih yd r oxyla tion of Styr en e: Rea ction Ra te P r ofile of
th e K
A 250 mL three-necked flask equipped with a magnetic stirring
bar and a pH electrode was charged with 4.14 g of K CO (17%
water), 78 mg (0.1 mmol) of ligand ((DHQD) PHAL), 14.7 mg
0.04 mmol) of K OsO ‚2H O, 85 mg (0.75 mmol) of NaClO
and 100 mL of H O/ BuOH (1:1) solution. The biphasic mixture
2 3 2
CO -Mod ified Na ClO Dih yd r oxyla tion (F igu r e 2).
2-P h en ylp r op a n e-1,2-d iol. The crude product was purified
by flash chromatography using a 2:1 solution of EtOAc/n-
hexane as the eluent. The yield was 1.11 g (73%). An analytical
sample of the product was obtained crystallization from
2
3
2
EtOAc: mp 43-45 °C (EtOAc) (lit.1 44-45 °C); H NMR (200
MHz, d-acetone) δ 7.50 (br, 2H), 7.25 (br, 3H), 3.99 (s, 1H),
3.81 (t, J ) 6 Hz, 1H), 3.58 (d, J ) 6 Hz, 2H), 1.48 (s, 3H);
0c
1
(
2
4
2
2
,
t
2
was cooled in an ice/water bath to 0-1 °C. Reaction was
initiated by adding 1 mmol of styrene to the reaction mixture
in one portion. A 100 µL aliquot was withdrawn from the
reaction mixture after 10, 20, 30, 50, 70, 90, 120, 180, 240,
and 360 s. The samples were then diluted with 2 mL of 0.5
mM diphenyl ether acetonitrile/water (7:3) solution. Samples
were analyzed with HPLC.
Dih yd r oxyla tion of Styr en e: Rea ction Ra te P r ofile of
th e Sh a r p less Asym m etr ic Dih yd r oxyla tion (F igu r e 2).
A 250 mL three-necked flask equipped with a magnetic stirring
bar and a pH electrode was charged with 0.988 g (3 mmol) of
9 12 2
HRMS m/z (M + Na) found 175.0728, calcd 175.0735 (C H O -
Na).
Hexa n e-1,2-d iol. The crude product was purified by flash
chromatography using a 2:1 solution of EtOAc/n-hexane as the
(
7) a
0 t
) initial concentration of styrene, a ) concentration of styrene
at a given time.
(8) (a) Sharpless, K. B.; Amberg, W.; Beller, M.; Chen, H.; Hartung,
J .; Kawanami, Y.; L u¨ bben, D.; Manoury, E.; Ogino, Y.; Shibata, T.;
Ukita, T. J . Org. Chem. 1991, 56, 4585-4588. (b) Kolb, H. C.;
VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483-
K
(
K
3
[Fe(CN)
0.1 mmol) of ligand ((DHQD)
2
OsO ‚2H O, and 100 mL of H O/ BuOH (1:1) solution. The
6
], 4.14 g (30 mmol) of K
2 3
CO (17% water), 78 mg
2
547 and references therein. (c) Becker, H.; King, S. B.; Taniguchi,
2
PHAL), 14.7 mg (0.04 mmol) of
M.; Vanhessche, K. P. M.; Sharpless, K. B. J . Org. Chem. 1995, 60,
3940-3941. (d) Sharpless, K. B.; Amberg, W.; Bennani, Y. L.; Crispino,
G. A.; Hartung, J .; J eong, K.-S.; Kwong, H.-L.; Morikawa, K.; Wang,
Z.-M.; Xu, D.; Zhang, X.-L. J . Org. Chem. 1992, 57, 2768-2771.
t
2
4
2
biphasic mixture was cooled in an ice/water bath to 0-1 °C.
Reaction was initiated by adding 1 mmol of styrene to the
reaction mixture in one portion. A 100 µL aliquot was
withdrawn from the reaction mixture after 20, 40, 60, 90, 120,
(9) (a) Styrene: Moreno-Dorado, F. J .; Guerra, F. M.; Ortega, M.
J .; Zubia, E.; Massanet, G. M. Tetrahedron: Asymmetry 2003, 14,
4
503-4510. (b) trans-Stilbene: Noe, C. R.; Knollmueller, M.; Stein-
1
80, 240, 360, 480, and 600 s. The samples were then diluted
bauer, G.; J angg, E.; Voellenkle, H. Chem. Ber. 1988, 121, 1231-1240.
with 2 mL of 0.5 mM diphenyl ether acetonitrile/water (7:3)
solution. Samples were analyzed with HPLC.
Dih yd r oxyla tion of Styr en e: Rea ction Ra te P r ofile of
th e Na OH-Mod ified Sh a r p less Asym m etr ic Dih yd r oxy-
la tion (F igu r e 2). A 250 mL three-necked flask equipped with
a magnetic stirring bar and a pH electrode was charged with
(c) R-Methyl styrene: Archelas, A.; Furstoss, R. J . Org. Chem. 1999,
6
4, 6112-6114. (d) 1-Hexene: Hung, S.-C.; Wen, Y.-F.; Chang, J .-W.;
Liao, C.-C.; Uang, B.-J . J . Org. Chem. 2002, 67, 1308-1313. (e)
1
-Hexadecen: Lafont, D.; Bouchu, M.-N.; Girard-Egrot, A.; Boullanger,
P. Carbohydr. Res. 2001, 336, 181-194. (f) Indene: Brooks, C. J . W.;
Young, L. Biochem. J . 1956, 63, 264-269. (g) 1-Methyl cyclohexene:
Tamura, Y.; Annoura, H.; Kondo, H.; Fuji, M.; Yoshida, T.; Fujioka,
H. Chem. Pharm. Bull. 1987, 35, 2305-2313. (h) Methyl trans-
cinnamate: Denis, J .-N.; Correa, A.; Greene, A. E. J . Org. Chem. 1990,
0
.988 g (3 mmol) of K
17% water), 2 mL of 1 M NaOH (2 mmol), 78 mg (0.1 mmol)
of ligand ((DHQD) PHAL), 14.7 mg (0.04 mmol) of K OsO
O, and 100 mL of H O/ BuOH (1:1) solution. The biphasic
3 6 2 3
[Fe(CN) ], 4.14 g (30 mmol) of K CO
(
5
5, 1957-1959.
2
2
4
‚
(10) (a) Brown, J . M.; Murrer, B. A. J . Chem. Soc., Perkin Trans. 2
t
2
H
2
2
1982, 489-498. (b) Hunter, D. H.; Cram, D. J . J . Am. Chem. Soc. 1966,
8
8, 5765-5776. (c) Fujisaka, T.; Miura, M.; Nojima, M.; Kusabayashi,
mixture was cooled in an ice/water bath to 0-1 °C. Reaction
was initiated by adding 1 mmol of styrene to the reaction
mixture in one portion. A 100 µL aliquot was withdrawn from
the reaction mixture after 20, 40, 60, 90, 120, 180, 240, 360,
S. J . Chem. Soc., Perkin Trans. 1 1989, 1031-1039. (d) Olah, G. A.;
Fung, A. P.; Meidar, D. Synthesis 1981, 4, 280-282. (e) Ohta, H.;
Tetsukawa, H. Agric. Biol. Chem. 1979, 43, 2099-2101. (f) Hamon,
D. P. G.; Tuck, K. L. Tetrahedron 2000, 56, 4829-4836. (g) Denis, J .-
N.; Correa, A.; Greene, A. E. J . Org.Chem. 1990, 55, 1957-1959.
4
80, 600 s. The samples were then diluted with 2 mL of 0.5
J . Org. Chem, Vol. 69, No. 14, 2004 4819