700
T. KOUSAKA and K. MORI
=
J
6.0 Hz, 3-H), 2.20 (2H, br, 1-OH and 2-OH),
(1R,2S)-(3
propanediol (
described for the preparation of 3, 12 (1.85 g,
? ?-Dichloro-4?-methoxyphenyl)-1,2-
,5
=
3.90 (3H, s, OCH3), 3.98 (1H, dq,
6.0 Hz, 2-H), 4.61 (1H, d,
J
4.2 and
4
). In the same manner as that
=
4.2 Hz, 1-H), 6.92
J
=
=
±
z) of ( )-4,
(1H, d,
2.0 Hz, 6
dC (75 MHz, CDCl3): 17.3 (C-3), 56.2 (OCH3), 71.1
(C-2), 76.6 (C-1), 111.8 (C-5 ), 122.4 (C-3 ), 126.1
(C-6 ), 128.5 (C-2 ), 133.5 (C-1 ), 154.5 (C-4 ).
These 13C-NMR data are in good agreement with
those reported for (
)-3.5) Anal. Found: C, 55.45;
H, 6.22 . Calcd. for C10H13ClO3: C, 55.44; H,
6.05
J
8.5 Hz, 5
?
-H), 7.22 (1H, dd,
J
8.5 and
8.52 mmol) was converted to 1.13 g (53
mp 98.5–107 C) and 0.63 g
C (lit.3) mp 100–102
) of („)-4 as colorless needles, mp 46–47 C,
1.45, CHCl3). IR nmax (nujol) cm„1
?-H), 7.39 (1H, d,
J
=
2.0 Hz, 2?-H)]. NMR
9
9
(29
z
„23.5 (
9
24
D
?
?
[
a
]
c
:
?
?
?
?
3270 (m, O–H), 3200 (m, O–H), 2925 (s), 2855 (s),
2360 (m), 1555 (m, Ar), 1480 (m, Ar), 1460 (m), 1425
(m), 1400 (m), 1375 (m), 1265 (m), 1210 (m), 1135
(m), 1095 (m), 1065 (m), 1020 (m), 1000 (m), 905 (w),
825 (m), 810 (m), 780 (m), 750 (m), 690 (m). GLC
±
z
z.
(Chirasil-DEX CB} column (0.25 mm 25 m) at
×
Methyl 3,5-dichloro-4-methoxybenzoate (10). In
the same manner as that described for the prepara-
tion of 6, 9 (1.00 g, 4.83 mmol) was converted to
80
9
C+1.5
9
C min to 200
9
z
C, He carrier gas at
), tR 59.8 min (1.1 ).
ee.
6.4 Hz,
W
90 kPa) tR
=
59.3 min (98.9
=
z
z
The enantiomeric purity of 1 was therefore 97.8
=
crude 10 (1.14 g, 99
z
) which was recrystallized from
NMR
d
H (500 MHz, CDCl3): 1.07 (3H, d,
J
C (lit.3)
3-H), 2.02 (1H, d,
J
3.4 Hz, 2-OH), 2.65 (1H, d,
=
hexane to give colorless needles, mp 78–79
9
82–83
9
C). IR nmax (ˆlm) cm„1: 1735 (s, C O), 1555
J
3.4 Hz, 1-OH), 3.87 (3H, s, OCH3), 3.99 (1H, m,
=
=
(m, Ar), 1480 (m, Ar), 1290 (s, C–O–C). NMR dH
2-H), 4.60 (1H, seemingly t,
(2H, s, 2 -H, 6 -H). NMR dC (125 MHz, CDCl3):
17.1 (C-3), 60.7 (OCH3), 70.9 (C-2), 76.0 (C-1),
127.1 (C-2 , C-6 ), 129.1 (C-3 , C-5 ), 138.0 (C-1 ),
151.4 (C-4
). These H- and 13C-NMR data are in
good agreement with those reported for (
)-4.5)
. Calcd. for
J 3.4 Hz, 1-H), 7.29
=
(500 MHz, CDCl3): 3.92 (3H, s, OCH3), 3.96 (3H, s,
?
?
CO2CH3), 7.98 (2H, s, 2?-H, 6?-H).
?
?
?
?
?
1
3,5-Dichloro-4-methoxybenzyl Alcohol (11). In the
same manner as that described for the preparation of
7, 10 (17.4 g, 73.5 mmol) was converted to 15.3 g (99
?
±
Anal. Found: C, 47.98; H, 4.74
z
z
46–47
) of 11 as colorless needles, mp 44–46
9
C (lit.3)
C10H12Cl2O3: C, 47.83; H, 4.82z.
9
C). IR nmax (ˆlm) cm„1: 3305 (m, O–H), 1560
(m, Ar), 1480 (m, Ar). NMR dH (400 MHz, CDCl3):
Acknowledgments
1.74 (1H, t,
4.63 (2H, d,
6?-H).
J
=
5.6 Hz, OH), 3.90 (3H, s, OCH3),
=
J
5.6 Hz, CH2O), 7.31 (2H, s, 2
?-H,
This work was ˆnancially supported by Mitsubishi
Chemical Co.
3,5-Dichloro-4-methoxybenzaldehyde (2). In the
References
same manner as that described for the preparation of
1) Gribble, G. W., Naturally occurring organohalogen
compounds. Acc. Chem. Res., 31, 141–152 (1998).
2) de Jong, E., Field, J. A., Dings, J. A. F. M.,
Wijnberg, J. B. P. A., and de Bont, J. A. M., De-novo
biosynthesis of chlorinated aromatics by the white-
rot fungus Bjerkandera sp. BOS55. Formation of
3-chloroanisaldehyde from glucose. FEBS Lett., 305,
220–224 (1992).
3) de Jong, E., Field, J. A., Spinnler, H.-E., Wijnberg,
J. B. P. A., and de Bont, J. A. M., Signiˆcant biogen-
esis of chlorinated aromatics by fungi in natural en-
vironments. Appl. Environ. Microbiol., 60, 264–270
(1994).
4) Brambilla, U., Nasini, G., and de Pava, O. V., Secon-
dary mold metabolites, Part 49. Isolation, structural
elucidation, and biomimetic synthesis of trametol, a
new 1-arylpropane-1,2-diol produced by the fungus
Trametes sp. J. Nat. Prod., 58, 1251–1253 (1995).
5) Swarts, H. J., Verhagen, F. J. M., Field, J. A., and
Wijnberg, J. B. P. A., Identiˆcation and synthesis of
1, 11 (2.70 g, 12.9 mmol) was converted to 2.60 g
(97
z) of 2 which was recrystallized from hexane to
9 9
give colorless needles, mp 62 C). IR
C (lit.3) 63–65
nmax (ˆlm) cm„1: 1695 (s, CHO), 1585 (m, Ar), 1555
(m, Ar). NMR dH (500 MHz, CDCl3): 3.99 (3H, s,
OCH3), 7.83 (2H, s, 2
?
-H, 6
?-H), 9.87 (1H, s, CHO).
(Z)-2,6-Dichloro-4-(1
?
-propenyl)anisole
(
12). In
the same manner as that described for the prepara-
tion of 8, 2 (5.86 g, 26.9 mmol) was converted to 5.85
1
=
g (E Z 1:2 by a H-NMR analysis, 95
z
) of 12. The
W
E Z mixture was separated several times by MPLC
W
to give 1.85 g (32
1.5161. IR
Ar), 1540 (m, Ar). NMR
z
) of 12 as a colorless oil, nD24
=
=
n
max (ˆlm) cm„1: 1645 (w, C C), 1590 (m,
d
H (300 MHz, CDCl3): 1.88
1.8 and 6.0 Hz, 3 -H), 3.90 (3H, s,
6.0 and 12.0 Hz, 2 -H),
1.8 and 12.0 Hz, 1 -H), 7.20 (2H, s,
C (100 MHz, CDCl3): 14.5 (C-3 ),
60.7 (OCH3), 127.1 (C-1 ), 128.7 (C-2 ), 128.8 (C-2,
C-6), 129.0 (C-3, C-5), 135.0 (C-4), 150.5 (C-1).
Anal. Found: C, 55.46; H, 4.91 . Calcd. for
C10H10Cl2O: C, 55.33; H, 4.64
=
(3H, dd,
OCH3), 5.83 (1H, dq,
6.26 (1H, dd,
3-H, 5-H). NMR
J
?
=
J
?
J
=
?
d
?
novel chlorinated p-anisylpropanoid metabolites from
Bjerkandera species. J. Nat. Prod., 61, 1110–1114
(1998).
?
?
6) Kolb, H. C., VanNieuwenhze, M. S., and Sharpless,
K. B., Catalytic asymmetric dihydroxylation. Chem.
z
z
.