1
990 J . Org. Chem., Vol. 62, No. 7, 1997
Shieh et al.
tetrahydrofuran, and hexane were dried with sodium ben-
zophenone and distilled before use. Dichloromethane was
(1.00 g, 1.86 mmol) was slowly added a CH
of NOBF
3
CN solution (1 mL)
(218 mg, 1.86 mmol) at 0 °C; after 30 min, to the
4
dried over CaH
2
and distilled before use. W(CO)
6
, p-toluene-
resulting solution was added NaI (550 mg, 3.72 mmol). The
mixture was allowed to stir for 6 h at 23 °C before treatment
with a saturated NaHCO (2 mL) solution. The organic layer
3
sulfonic acid, dicyclopentadiene, propargyl alcohol, and sodium
were obtained commercially and used without purification. The
syntheses of organic substrates 1 and 5-12 were described in
was extracted with diethyl ether (2 × 5 mL), concentrated,
7
our previous paper. Syntheses and spectral data of com-
and eluted on a preparative TLC plate (diethyl ether/hexane
pounds of the same family 14-20 and 22-27 in the repetitive
operations, are listed in the Supporting Information.
Elemental analyses were performed at National Cheng
Kung University, Taiwan. Mass data of molybdenum and
) 1/1) to give 4 as an oil (R ) 0.50, 224 mg, 1.12 mmol, 60%):
f
-
1
1
3
IR (neat, cm ) υ(CO) 1768, 1660; H NMR (400 MHz, CDCl )
δ 7.24-7.12 (m, 4H), 6.25 (d, J ) 2.8 Hz, 1H), 5.59 (d, J ) 2.4
Hz, 1H), 5.06 (ddd, J ) 8.2, 7.8, 4.2 Hz, 1H), 4.28 (dt, J ) 7.8,
9
6
184
13
tungsten compounds were reported according to Mo and
isotopes.
W
2.7 Hz, 1H), 2.66 (m, 2H), 2.19 (m, 1H), 1.85 (m, 1H); C NMR
(100 MHz, CDCl ) δ 170.2, 138.8, 136.8, 134.5, 128.7, 127.2,
3
Gen er a l P r oced u r e for th e Syn th eses of Tu n gsten -
12 2
126.9, 123.3, 42.5, 28.3, 24.5; HRMS calcd for C13H O
3
η -3-(Meth oxyca r bon yl)a llyl Com p ou n d s. Syn th esis of
. A suspension of W(CO) (2.86 g, 8.00 mmol) and NaC
0.71 g, 8.0 mmol) in THF (30 mL) was heated for 84 h. To a
THF solution (5.0 mL) of 1 (2.00 g, 8.00 mmol) was added
dropwise the above CpW(CO) Na solution in three portions
200.0837, found 200.0841.
3
(
6
5
H
5
3
Syn th esis of Tu n gsten -η -a llyl Com p ou n d 13. NaCp-
W(CO)
3
(1.435 mmol), 2-(6-bromohex-4-ynyl)-1,3-dioxolane (5)
(
3
1
1.00 g, 4.31 mmol), and p-TSA/CH OH afforded 13 (1.68 g,
3
-1
3
.53 mmol) in 82% yield: IR (neat, cm ) υ(CO) 1958, 1886,
1
at 30-min intervals. Monitoring the solution by silica TLC
708; H NMR (400 MHz, CDCl , -40 °C) δ 9.73 (t, J ) 2.0
3
1
showed the formation of an η -propargyl species 2 (diethyl
Hz, 1H), 5.27 (s, 5H), 3.61 (s, 3H), 2.83 (s, 1H), 2.61 (m, 1H),
.52 (dt, J ) 7.5, 2.0 Hz, 1H), 2.20 (m, 1H), 2.05 (t, J ) 7.2
ether/hexane ) 1/1, R ) 0.82). The solution was stirred for 2
f
2
h at the same temperature before it was evaporated to dryness
13
Hz, 1H), 1.62 (quintet, J )7.2 Hz, 2H), 1.06 (s, 1H); C NMR
1
in vacuo. The η -propargyl species was extracted with diethyl
(100 MHz, CDCl
3
, -40 °C) δ 224.3, 222.9, 203.4, 171.2, 88.0,
ether (2 × 20 mL), filtered, and dried in vacuo. To the residue
were added MeOH (20 mL) and p-toluenesulfonic acid (152
mg, 0.80 mmol) at 0 °C, and the mixture was stirred for 2 h
before being dried in vacuo. The residues were redissolved in
an acetone/water mixing solvent (v/v 10/1, 20 mL) containing
additional p-TSA (150 mg, 0.80 mmol), and the mixture was
+
7
4
WO
7.3, 51.1, 50.1, 43.7, 31.9, 25.1, 22.7; MS (EI, 12 eV) 474 (M ),
+
+
46 (M - CO), 418 (M - 2CO). Anal. Calcd for C16
: C, 40.53; H, 3.83. Found: C, 40.66; H, 3.88.
Syn th esis of 2-Meth ylen e-4-oxa bicyclo[3.3.0]octa n -3-
on e (21). Compound 13 (0.50 g, 1.05 mmol), NOBF (123 mg,
.05 mmol), and NaI (315 mg, 2.10 mmol) afforded 21 (77 mg,
18
H -
5
4
1
5
heated at 80 °C for 2 h before a saturated NaHCO
was added. The organic layer was extracted with diethyl ether
3 × 25 mL), dried over MgSO , and concentrated. The
3
solution
-1
1
3%) as a colorless oil: IR (neat, cm ) 1757.8, 1658.6; H NMR
) δ 6.22 (d, J ) 2.6 Hz, 1H), 5.67 (d, J ) 2.6
Hz, 1H), 4.96 (t, J ) 6.8 Hz, 1H), 3.39 (dt, J ) 6.8 Hz, 2.2 Hz,
(400 MHz, CDCl
3
(
4
residues were chromatographed through a silica column to
1
1
4
1
H), 2.08 (m, 1H), 1.94 (m, 1H), 1.74-1.65 (m, 3H), 1.50 (m,
-
1
yield 3 as a yellow oil (2.91 g, 5.44 mmol, 68%): IR (neat, cm
)
)
13
H); C NMR (100 MHz, CDCl
2.9, 35.6, 33.6, 23.0; HRMS cacld for C
36.0680. The NMR and IR spectral data of 21 were identical
3
) δ 171.2, 140.5, 122.7, 83.2,
1
υ(CO), 1966.3, 1898.9, 1722.1724; H NMR (400 MHz, CDCl
3
8
10 2
H O
138.0680, found
endo isomer, δ 9.72 (1H, d, J ) 4.0 Hz), 7.24-7.12 (m, 4H),
5
1
9
.42 (5H, s), 3.48 (3H, s), 3.20 (m, 1H), 3.18 (s, 1H), 3.00 (s,
H), 2.95 (m, 1H), 2.70 (m, 2H), 1.48 (s, 1H); exo isomer, δ
.72 (1H, d, J ) 4.0 Hz), 7.24-7.12 (m, 4H), 5.46 (5H, s), 3.58
8
to those of the authentic sample reported in literature.
(3H, s), 3.20 (m, 1H), 2.95 (m, 1H), 2.93 (s, 1H), 2.70 (m, 2H),
Ack n ow led gm en t. The authors thank the National
Science Council, ROC, for financial support of this work.
1
3
2
.60 (s, 1H), 0.92 (s, 1H); C NMR (100MHz, CDCl
3
) exo and
endo isomers, δ 223.6, 223.7, 223.2, 219.3, 203.3, 202.9, 173.2,
1
1
5
5
70.8, 140.2, 139.9, 139.6, 137.1, 135.8, 134.7, 129.2, 128.8,
27.7, 127.4, 127.2, 126.6, 93.9, 89.2, 79.1, 70.3, 64.5, 61.0, 53.6,
2.4, 51.6, 44.5, 44.3, 27.5, 26.4, 26.1, 23.2; MS (EI, 12 eV)
Su p p or tin g In for m a tion Ava ila ble: Syntheses and spec-
tral data of compounds of the same family 14-20 and 22-27
in the repetitive operations (6 pages). This material is
contained in libraries on microfiche, immediately follows this
article in the microfilm version of the journal, and can be
ordered from the ACS: see any current masthead page for
ordering information.
+
+
+
36 (M ), 508 (M - CO), 480 (M - 2CO). Anal. Calcd for
: C, 47.04; H, 3.76. Found: C, 47.02; H, 3.77.
Gen er a l P r oced u r e for t h e Syn t h eses of F u sed r-
Meth ylen ebu tyr ola cton es. Syn th esis of 1-Meth ylen e-
a ,4,5,9b-tetr a h yd r o-1H-n a p h th o[2,1-b]fu r a n -2-on e (4).
To a stirring CH CN (5 mL) solution of π-allyl compound 3
21 5
C H20WO
3
3
J O961936M