2
1
7
.27 (t, J ) 2.3 Hz, 1H); 13C NMR (125 MHz, CDCl
, 70 °C) δ
3
70.8, 161.5, 141.7, 136.9, 129.3, 128.6, 117.2, 114.8, 114.0, 79.6,
2.3, 54.8, 48.0 (br s), 37.0 (br s); IR (neat) 3292, 2118, 1638
-
1
+
cm ; LRMS (EI) m/z 255 (M , 49), 135 (100); HRMS calcd for
C
+
16
H
17NO
2
(MH ) 255.1259, found 255.1260.
5
-(ter t-Bu tyld im eth ylsilyl)-4-p en tyn -1-ol (11): clear liq-
1
uid; H NMR (300 MHz, CDCl
3
) δ 3.77 (q, J ) 5.8 Hz, 2H), 2.36
3
-Bu tyl-7-(ter t-bu tyld im eth ylsilyloxy)tr icyclo[4.3.1.01,6]-
d eca -2,4-d ien e (16). A 1D NOE difference experiment on 16a
a clear, pale yellow liquid) exhibited a 5.8% enhancement of
when H was irradiated. Assignment of proton and carbon
atoms was based on COSY, HETCOR, and DEPT experiments:
(
5
t, J ) 6.9 Hz, 2H), 1.78 (pentet, J ) 6.4 Hz, 2H), 1.56 (t, J )
.3 Hz, 1H), 0.92 (s, 9H), 0.08 (s, 6H) ppm; 1 C NMR (125 MHz,
3
(
H
CDCl
IR (neat) 3329, 2178 cm ; LRMS (EI) m/z 141 (9), 75 (100).
-(ter t-Bu tyld im eth ylsilyl)-4-p en tyn a l (12): clear, citrus-
3
) δ 107.2, 83.4, 61.9, 31.2, 26.0, 16.44, 16.39, -4.6 ppm;
-
1
b
a
5
1
1
H NMR (500 MHz, CDCl
d, J ) 8.8 Hz, 1H), 5.70 (s, 1H), 4.32 (t, J ) 7.8 Hz, 1H), 2.11-
2.02 [(m, 3H) containing 2.06 (t, J ) 7.5 Hz, 2H)], 1.71 (dt, J )
3.2, 8.3 Hz, 1H), 1.59 (ddd, J ) 12.2, 8.8, 2.0 Hz, 1H), 1.40-
1.34 (m, 2H), 1.26 (apparent sextet, J ) 7.3 Hz, 2H), 0.91 (s,
H), 0.88 (t, J ) 7.1 Hz, 3H), 0.09 (s, 3H), 0.05 (s, 3H), -0.38 (d,
3
) 16a δ 6.24 (d, J ) 9.3 Hz, 1H), 5.71
smelling oil; H NMR (300 MHz, CDCl
3
) δ 9.79 (t, J ) 1.0 Hz,
(
1
H), 2.70-2.64 (m, 2H), 2.57-2.52 (m, 2H), 0.91 (s, 9H), 0.07
1
3
(s, 6H) ppm; C NMR (125 MHz, CDCl
3
) δ 200.6, 105.3, 84.0,
1
4
2.6, 25.9, 16.4, 13.1, -4.7 ppm; IR (neat) 2855, 2724, 2176, 1731
-
1
cm ; LRMS (EI) m/z 139 (100), 109 (45), 57 (7).
9
8
-(ter t-Bu tyld im eth ylsilyl)-3-m eth ylen eoct-1-en -7-yn -4-
1
3
1
J ) 3.9 Hz, 1H) ppm; C NMR (125 MHz, CDCl
3
) 16a δ 131.5,
3
ol (13): clear, yellow oil; H NMR (300 MHz, CDCl ) δ 6.38 (dd,
1
2
1
28.0, 124.1, 122.8, 77.3, 39.5, 35.3, 35.2, 31.4, 29.7, 29.0, 25.9,
2.1, 18.1, 13.9, 12.7, -4.59, -4.62 ppm; 16b δ 131.9, 127.8,
22.9, 122.7, 75.8, 39.5, 34.5, 32.6, 31.5, 30.8, 29.9, 25.7, 22.6,
J ) 17.9, 11.2 Hz, 1H), 5.37 (d, J ) 17.9 Hz, 1H), 5.31 (s, 1H),
5
2
0
1
.17 (s, 1H), 5.11 (d, J ) 11.2 Hz, 1H), 4.66-4.64 (m, 1H), 2.51-
.27 (m, 2H), 1.98-1.85 (m, 2H), 1.77-1.65 (m, 1H), 0.93 (s, 9H),
-
1
1
3
22.1, 15.9, 14.0, -4.5, -4.8 ppm; IR (neat) 1269 cm ; LRMS
3
.09 (s, 6H) ppm; C NMR (125 MHz, CDCl ) δ 148.8, 136.2,
+
(EI) m/e 318 (M , 17), 260 (100), 186 (70), 129 (74); HRMS (EI)
14.43, 114.39, 107.4, 83.5, 70.1, 35.1, 26.0, 16.5, 16.4, -4.6 ppm;
+
-
1
+
4
,
calcd for C20
H35OSi (MH ) 319.2449, found 319.2457. Anal. Calcd
IR (neat) 3365, 2173 cm ; LRMS (CI, NH
3
) m/z 268 (MNH
8), 251 (MH , 82); HRMS (MH ) calcd for C15 27OSi 251.1831,
found 251.1834.
-Met h ylen e-5-(ter t-b u t yld im et h ylsilyloxy)-7-en -1-yn e
+
+
for C20 34OSi: C, 75.42; H, 10.77. Found: C, 75.08; H, 10.44.
H
1
H
1
,6
Dim eth yl 3-m eth yltr icyclo[4.3.1.0 ]d eca -2,4-d ien e-8,8-
d ica r boxyla te (17): clear, colorless liquid; H NMR (300 MHz,
1
6
CDCl ) δ 6.13 (d, J ) 9.4 Hz, 1H), 5.82 (s, 1H), 5.67 (d, J ) 9.4
3
1
(
(
1
3
1
3
14): clear, colorless liquid; H NMR (300 MHz, CDCl ) δ 6.31
Hz, 1H), 3.76 (s, 3H), 3.68 (s, 3H), 2.87 (d, J ) 13.4, 2H), 2.41
dd, J ) 17.9, 11.2 Hz, 1H), 5.36 (d, J ) 17.9 Hz, 1H), 5.23 (s,
(
(
1
1
3
2
d, J ) 13.5 Hz, 2H), 1.82 (s, 3H), 1.24 (d, J ) 4.7 Hz, 1H), -0.21
d, J ) 4.7 Hz, 1H); 13C NMR (125 MHz, CDCl
) δ 173.1, 172.0,
28.9, 127.0, 123.5, 123.4, 59.0, 52.9, 41.4, 41.1, 36.0, 29.6, 21.3,
H), 5.11 (s, 1H), 5.07 (d, J ) 11.3 Hz, 1H), 4.53 (dd, J ) 7.8,
.6 Hz, 1H), 2.37-2.16 (m, 2H), 1.95 (t, J ) 2.5 Hz, 1H), 1.88-
3
.65 (m, 2H), 0.90 (s, 9H), 0.08 (s, 3H), 0.00 (s, 3H) ppm; 13
C
-
1
+
8.9 ppm; IR (thin film) 1737, 1690 cm ; LRMS m/e 262 (M ,
NMR (100 MHz, C
6 6
D ) δ 149.2, 136.3, 115.0, 114.2, 84.2, 71.3,
+
), 143 (100); HRMS calcd for C15
62.1273.
18 4
H O (MH ) 262.1283, found
6
9.4, 37.2, 26.3, 18.7, 15.5, -4.2, -4.7 ppm; IR (neat) 3317, 2121
-
1
+
+
cm ; LRMS (CI, NH
3
) m/z 268 (MNH
4
, 94), 251 (MH , 100);
(
5â)-N-(4-Tolu en esu lfon yl)-1â-(2-oxoh exyl)-5â-vin yl-3-
+
HRMS (MH ) calcd for C15 27OSi 251.1831, found 251.1833.
H
1
a za bicyclo[3.1.0]h exa n e (18a ): clear, pale yellow oil; H NMR
300 MHz, CDCl ) δ 7.68 (d, J ) 8.1 Hz, 2H), 7.32 (d, J ) 8.1
Hz, 2H), 5.59 (dd, J ) 17.2, 10.6 Hz, 1H), 5.07 (d, J ) 10.2 Hz,
H), 4.98 (d, J ) 17.0 Hz, 1H), 3.66 (d, J ) 9.1 Hz, 1H), 3.58 (d,
J ) 9.1 Hz, 1H), 3.19 (d, J ) 9.2 Hz, 1H), 2.94 (d, J ) 9.2 Hz,
H), 2.44 (d, J ) 17.4 Hz, 1H), 2.43 (s, 3H), 2.34 (d, J ) 17.4
Hz, 1H), 2.32 (t, J ) 7.4 Hz, 2H), 1.48 (pentet, J ) 7.5 Hz, 2H),
.25 (sextet, J ) 7.6 Hz, 2H), 1.02 (d, J ) 5.6 Hz, 1H), 0.87 (t,
Gen er a l P r oced u r e for Ca r ben e Cycliza tion s. A solution
of the carbene complex (0.60 mmol) and the dienyne (0.50 mmol)
in benzene or THF (10.0 mL) were heated until disappearance
of the dienyne was observed by TLC. The reaction mixture was
then concentrated in vacuo, and the remaining material was
immediately purified by silica gel chromatography.
(
3
1
1
1
,6
Dim eth yl 3-bu tyltr icyclo[4.3.1.0 ]d eca -2,4-d ien e-8,8-d i-
1
1
ca r boxyla te (15a ): clear, colorless liquid; H NMR (300 MHz,
1
3
J ) 7.3 Hz, 3H), 0.75 (d, J ) 5.5 Hz, 1H) ppm; C NMR (125
MHz, CDCl ) δ 208.9, 143.6, 134.7, 133.8, 129.8, 127.6, 115.9,
3.2, 52.4, 43.0, 42.4, 33.1, 30.2, 25.6, 22.1, 21.4, 17.9, 13.7 ppm;
CDCl
3
) δ 6.12 (d, J ) 9.4 Hz, 1H), 5.80 (s, 1H), 5.69 (d, J ) 9.4
3
Hz, 1H), 3.76 (s, 3H), 3.67 (s, 3H), 2.82 (d, J ) 13.4 Hz, 2H),
5
2
.41 (d, J ) 13.5 Hz, 2H), 2.05 (t, J ) 7.3 Hz, 2H), 1.48-1.20
-
1
IR (KBr) 1714, 1341, 1161, 1099, 999, 814 cm ; LRMS (CI, NH
m/z 362 (M , 100); HRMS calcd for C20
3
)
(
m, 5H), 0.90 (t, J ) 7.1 Hz, 3H), -0.24 (d, J ) 4.5 Hz, 1H) ppm;
+
+
H
28NO
3
S (MH ) 362.1790,
1
3
C NMR (125 MHz, CDCl
3
) δ 173.0, 171.9, 131.7, 128.8, 123.1,
found 362.1805.
1
1
22.6, 59.1, 52.8, 41.4, 41.1, 35.9, 35.19, 35.15, 31.2, 22.1, 19.1,
3.8; IR (neat) 1737 cm ; LRMS (CI, CH
(
5â)-N-(4-Met h oxyb en zoyl)-1â-(2-oxoh exyl)-5â-vin yl-3-
-
1
+
4
) m/z 305 (MH , 38);
1
a za bicyclo[3.1.0]h exa n e (18b): clear, colorless oil; H NMR
300 MHz, C , 70 °C) δ 7.49 (d, J ) 8.6 Hz, 2H), 6.67 (d, J )
.6 Hz, 2H), 5.63 (dd, J ) 17.3, 10.8 Hz, 1H), 4.99 (d, J ) 10.7
+
HRMS calcd for C18
Diet h yl 3-bu t ylt r icyclo[4.3.1.0 ]d eca -2,4-d ien e-8,8-d i-
ca r boxyla te (15b): clear, pale yellow liquid; H NMR (400
25 4
H O (MH ) 305.1753, found 305.1769.
(
8
6 6
H
1
,6
1
Hz, 1H), 4.96-4.85 (m, 1H), 3.63 (t, J ) 10.7 Hz, 2H), 3.28 (s,
MHz, CDCl
9.6 Hz, 1H), 4.20 (q, J ) 7.2 Hz, 2H), 4.11 (q, J ) 7.2 Hz, 2H),
.82 (dd, J ) 13.2, 2.4, 2H), 2.41 (dd, J ) 13.6, 5.6 Hz, 2H), 2.06
t, J ) 7.2 Hz, 3H), 1.28-1.17 (m, 10H), 0.87 (t, J ) 7.2 Hz,
3
) δ 6.12 (d, J ) 9.2 Hz, 1H), 5.79 (s, 1H), 5.67 (d, J
3
1
0
1
H), 3.16 (s, 2H), 1.96-1.83 (m, 2H), 1.34-1.27 (m, 3H), 1.24-
.17 (m, 2H), 0.96 (d, J ) 5.0 Hz, 1H), 0.90 (d, J ) 4.9 Hz, 1H),
)
2
6 6
.81 (t, J ) 7.3 Hz, 3H), 0.25 (s, 1H); IR (C H solution) 1631,
(
-
1
+
610 cm ; LRMS (EI) m/z 342 (M , 28), 324 (14), 135 (100);
3
1
3
H), -0.26 (d, J ) 4.4 Hz, 1H); 13C NMR (100 MHz, CDCl
3
) δ
+
3
HRMS calcd for C21H28NO (MH ) 342.2071, found 342.2069.
72.2, 171.1, 131.4, 128.7, 123.0, 122.4, 61.7, 59.2, 41.4, 41.0,
6.2, 35.5, 35.4, 31.4, 22.3, 19.4, 14.2 14.1 ppm; IR (neat) 1730
-
1
+
Ack n ow led gm en t. We are grateful for support from
the National Institutes of Health (Grant GM41984).
T.M.B. is a Lucille Markey scholar. We would also like
to thank Professor Kenneth J . Shea for many helpful
discussions.
cm ; LRMS m/e 332 (M , 43), 258 (100); HRMS (EI) m/e calcd
for C20
28 4
H O 332.1987, found 332.1987.
Diben zyl 3-Bu tyltr icyclo[4.3.1.0 ,6]d eca -2,4-d ien e-8,8-d i-
1
ca r boxyla te (15c). Rapid degradation of 15c prevented the
calculation of an accurate yield; however, the following crude
1
spectroscopic data were obtained: H NMR (400 MHz, CDCl
3
)
δ 7.32-7.20 (m, 10H), 6.10 (d, J ) 9.2 Hz, 1H), 5.76 (s, 1H),
Su p p or t in g In for m a t ion Ava ila b le: 1H and 13C NMR
spectra for 7a -c, 9a ,b, 11-14, 15a -c, 16, 17, and 18a ,b. This
material is available free of charge via the Internet at
http://pubs.acs.org.
5
1
7
.65 (d, J ) 9.6 Hz, 1H), 5.11 (s, 2H), 5.02 (s, 2H), 2.84 (dd, J )
3.5, 2.4 Hz, 2H), 2.43 (dd, J ) 13.4, 5.5 Hz, 2H), 1.36-1.09 (m,
H), 0.86 (t, J ) 7.2 Hz, 3H), -0.27 (d, J ) 4.4 Hz, 1H) ppm; IR
-1
+
(neat) 1816, 1735 cm ; LRMS m/e 456 (M , 4), 413 (100); HMRS
FAB) m/e calcd for C30 Na 479.2198, found 479.2212.
(
H
32
O
4
J O020378A
8
678 J . Org. Chem., Vol. 67, No. 24, 2002