GEMINAL DIMETHYL-SUBSTITUTED FUNCTIONALIZED C -SYNTHONS
697
4
of p-toluenesulfonic acid at 0 C. Yield 1.5 g (91%).
spectrum (CDCl ), , ppm: 19.85 and 20.75 (CH ),
3
C
4
3
2
3
1
The product was isolated as a mixture of diastereo-
3
5.19 (C ), 43.85 (C ), 58.12 (C ), 69.59 (C ).
,2-Dimethyl-1-(2-tetrahydrofuryloxy)-3,4-
1
isomers at a ratio of 1:2. IR spectrum, , cm : 745,
2
9
40, 1085, 1140, 1390, 1460, 1480, 1800, 2380.
epoxybutane (VIII) was synthesized as described
above for compound V from 0.12 g (1.03 mmol) of
epoxy derivative VII and 0.14 g (2.06 mmol) of
dihydrofuran in 5 ml of dry methylene chloride con-
taining 3 mg of p-toluenesulfonic acid. Product VIII
was isolated as a mixture of diastereoisomers by
Found, %: C 59.88; H 7.90. C H O . Calculated, %:
C 60.00; H 8.00. H NMR spectrum (CDCl ), , ppm:
1
0
16
4
1
3
major isomer: 0.99 s and 1.11 s (6H, CH ), 1.77
3
2
4
.04 m (4H, CH ), 3.79 3.98 m (4H, OCH ) and
.06 s (1H, OCH), 5.51 d (1H, OCHO, J = 4.23 Hz);
2 2
minor isomer: 1.01 s and 1.16 s (6H, CH ), 1.77
3
column chromatography on silica gel. Yield 0.1 g
2
4
.04 m (4H, CH ), 3.79 3.98 m (4H, OCH ) and
2 2
1
(
54%). IR spectrum, , cm : 880, 940, 1005, 1070,
.15 s (1H, OCH), 5.21 d (1H, OCHO, J = 4.18 Hz).
1
3
1135, 1215, 1380, 1480. Found, %: C 63.90; H 9.90.
C NMR spectrum (CDCl3), C, ppm: major isomer:
1
C H O . Calculated, %: C 64.52; H 9.68. H NMR
1
9.39 and 22.80 (CH ), 23.08 and 32.13 (CH , THF),
10 18
3
3
2
spectrum (CDCl ), , ppm: major isomer: 0.82 s and
3
4
3
3
9.89 (C ), 67.19 (OCH , THF), 76.21 (C ), 77.45
2
2
0.83 s (6H, CH3), 1.70 2.00 (4H, CH2), 2.59 d
(
C ), 103.07 (OCHO), 175.68 (C O); minor isomer:
(
2H, OCH , J = 3.50 Hz), 2.85 t (1H, OCH, J =
2
1
9.39 and 23.38 (CH ), 22.76 and 32.30 (CH , THF),
3 2
3
.50 Hz), 3.42 d (1H, J = 9.2 Hz) and 3.48 d (1H,
3
4
4
0.21 (C ), 67.36 (OCH , THF), 75.57 (C ), 77.87
2
OCH , J = 9.2 Hz), 3.82 t (2H, OCH , THF, J =
2
2
2
(
C ), 104.07 (OCHO), 175.05 (C O).
,3-Dimethyl-2-methylsulfonyloxy-1,4-butane-
diol (VI) and 2,2-dimethyl-3,4-epoxy-1-butanol
VII). To a suspension of 2.05 g (53.5 mmol) of
6
.60 Hz), 5.04 d.d (1H, OCHO, J = 2.5, 5.3 Hz);
3
minor isomer: 0.83 s and 0.85 s (6H, 2CH ), 1.70
3
2
2
.00 (4H, CH ), 2.61 d (2H, CH O, J = 3.50 Hz),
.82 t (1H, OCH, J = 3.50 Hz), 3.09 d.d (1H, J =
2 2
(
NaBH in 30 ml of anhydrous MeOH at 0 C we added
4
9.3 Hz) and 3.12 d (1H, OCH , J = 9.3 Hz), 3.82 t
2
dropwise a solution of 1 g (5.1 mmol) of compound
III in 3 ml of MeOH. The mixture was stirred for
(
4
2H, OCH , THF, J = 6.60 Hz), 5.39 d (1H, J =
.58 Hz, OCHO). C NMR spectrum (CDCl3), C,
2
1
3
4
h at that temperature, excess NaBH was decom-
4
ppm: major isomer: 20.34 and 20.46 (CH ), 23.47 and
3
posed with a small amount of a saturated solution
2
4
3
3
6
2.24 (CH , THF), 34.68 (C ), 43.97 (C ), 57.40 (C ),
6.75 (C ), 73.49 (OCH , THF), 103.96 (OCHO);
2
of NH Cl, methanol was distilled off, and the products
4
1
2
were extracted into ethyl acetate (3 20 ml). The
combined organic extracts were dried over MgSO4
and evaporated, and the residue was subjected to
column chromatography on silica gel using ethyl
acetate benzene (1:1) as eluent. We isolated 0.4 g
minor isomer: 20.22 and 20.63 (CH ), 23.41 and
3
6
3
2
4
3
2.24 (CH , THF), 34.68 (C ), 44.03 (C ), 57.22 (C ),
6.99 (C ), 73.59 (OCH , THF), 103.79 (OCHO).
2
1
2
2,2-Dimethyl-1-(2-tetrahydrofuryloxy)hexan-3-
(
38%) of compound VI and 0.25 g (42%) of epoxy
ol (IX). To a solution of 0.1 g (0.56 mmol) of com-
pound VIII in 10 ml of anhydrous THF at 0 C we
added dropwise 0.7 ml of a 2.9 N solution of EtMgBr
derivative VII.
1
Compound VI. IR spectrum, , cm : 830, 870,
(
2 mmol) in THF. The mixture was stirred for 30 min
9
40, 1075, 1180, 1345, 2905, 3380 3540 (OH).
1
at 0 C and for 3 h at 45 50 C (TLC monitoring). It
H NMR spectrum (CDCl ), , ppm: 0.92 s and 0.98 s
3
was decomposed with a saturated solution of NH Cl,
(
6H, CH ), 3.15 s (3H, SO CH ), 3.17 br.s (2H, OH),
4
3
2
3
tetrahydrofuran was distilled off, the residue was
extracted with ethyl acetate (3 10 ml), and the extract
3
.31 d (1H, J = 11.54 Hz) and 3.47 d (1H, OCH2,
2
J = 11.54 Hz), 3.79 d.d (1H, J = 7.00, 12.60 Hz) and
.92 d.d (1H, OCH , J = 2.8, 12.60 Hz), 4.66 d.d
was dried over MgSO and evaporated. The residue
4
3
2
1
3
was subjected to column chromatography on silica gel
using ethyl acetate petroleum ether (1:1) as eluent
to isolate 0.06 g (52%) of compound IX as an oily
(1H, OCH, J = 2.80, 7.08 Hz). C NMR spectrum
(CDCl3), , ppm: 20.17 and 21.82 (CH ), 38.65
(SO CH ), 38.98 (C ), 61.48 (C ), 68.23 (C ),
C
3
3
1
4
2
3
1
2
substance. IR spectrum, , cm : 1125, 1285, 1325,
8
8.51 (C ).
1
1
380, 1465, 1670. H NMR spectrum (CDCl ), ,
1
3
Compound VII. IR spectrum, , cm : 864, 1072,
ppm: 0.82 s and 1.04 s (6H, CH ), 0.87 t (3H, CH ,
1
3
3
1
156, 1212, 1368, 1456, 3448, 3600. H NMR spec-
J = 7.80 Hz), 1.26 m (2H, CH ), 1.70 1.86 m (4H,
2
trum (CDCl ), , ppm: 0.78 s and 0.91 s (6H, CH ),
2
2
3
3
CH ), 1.91 br.s (1H, OH), 3.29 t (1H, OCH, J =
2
.65 d (2H, OCH , J = 3.30 Hz), 2.80 br.s (1H, OH),
2
10.28 Hz), 3.39 d (1H, J = 11.2 Hz), 3.55 d (1H,
OCH , J = 11.2 Hz), 3.69 t (2H, OCH , THF, J =
.84 t (1H, OCH, J = 3.30 Hz), 3.29 d (1H, J =
2
2
1
3
1
1.0 Hz), 3.39 d (1H, CH O, J = 11.0 Hz). C NMR
6.01 Hz), 4.61 d.d (1H, OCHO, J = 4.22, 4.80 Hz).
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 5 2001