8520 J . Org. Chem., Vol. 62, No. 24, 1997
Mash et al.
(1S,2R,12S)-2-Bu tylbicyclo[10.1.0]tr id ec-3-en -2-ol (7a ).
From n-butyllithium (0.90 mmol) and E-4 (58 mg, 0.30 mmol)
was obtained 71 mg (0.21 mmol, 94%) of 7a , Rf 0.47 (10%
EtOAc/hexanes), as a colorless oil. Spectral data appear in
the Supporting Information.
(1S,2R,15S)-2-Bu tylbicyclo[13.1.0]h exadec-3-en -2-ol (8a).
From n-butyllithium (0.85 mmol) and E-5 (67 mg, 0.29 mmol)
was obtained 61 mg (0.21 mmol, 74%) of 8a , Rf 0.42 (10%
EtOAc/hexanes), as a colorless oil. Spectral data appear in
the Supporting Information.
m), 1.32-1.70 (4, m), 1.78-1.96 (2, m), 2.13-2.25 (1, m), 2.27-
2.36 (1, m), 2.43 (1, t, J ) 10.6 Hz); 13C NMR δ 8.1, 19.2, 24.4,
25.7, 27.5, 29.2, 32.4, 34.1, 59.3, 210.4.
(1R,4R,8S)-4-P h en ylb icyclo[6.1.0]n on a n -2-on e (16a ).
From CuI (66 mg, 0.35 mmol), phenyllithium (0.65 mL of a
1.4 M solution, 0.91 mmol), and enone Z-3 (31 mg, 0.23 mmol)
was obtained 49 mg (0.22 mmol, 95%) of 16a , Rf 0.46 (20%
EtOAc/hexanes), as white crystals, mp 82-85 °C, after chro-
matography on silica gel 60 (240-400 mesh) eluted with 10%
Et2O/hexanes. Spectral data appear in the Supporting Infor-
mation.
(1R,3R,5S,9S)-Tr icyclo[7.1.0.03,5]decan -2-on e (12a). Pen-
tane-washed NaH (15 mg, 80% in oil, 0.50 mmol) was
suspended in DMSO (0.5 mL) in a water bath at rt. After 30
min trimethyloxosulfonium iodide (88 mg, 0.40 mmol) was
added. After 15 min, a solution of enone Z-3 (49 mg, 0.36
mmol) in DMSO (1 mL) was added via cannula and the
mixture was heated to 50 °C for 15 min. The mixture was
cooled and quenched with water (10 mL), and the aqueous
phase was extracted with pentane. The organic extracts were
dried (MgSO4) and filtered, and volatiles were removed. The
residue was chromatographed on silica gel (240-400 mesh,
25 g) eluted with 20% Et2O/pentane to give 44 mg (0.29 mmol,
80%) of 12a , Rf 0.20 (20% Et2O/pentane), as a colorless liquid.
Sp ectr a l d a ta for 12a : [R]24D +41 (c 2.18, CHCl3); IR (neat)
cm-1 1661; 1H NMR δ 1.00-1.42 (8, m), 1.55-1.70 (2, m),
1.79-1.90 (2, m), 2.02-2.15 (2, m); 13C NMR δ 12.4, 18.9, 24.9,
25.5, 27.5, 209.1; HRMS (EI) calcd for C10H14O 150.1045, found
150.1045.
The structure of 16a was established by single-crystal X-ray
analysis.21
(1S,4R,12S)-4-Meth ylbicyclo[10.1.0]tr idecan -2-on e (17a).
From CuI (199 mg, 1.0 mmol), methyllithium (4.4 mL of a 0.45
M solution, 2.0 mmol), and enone E-4 (95 mg, 0.50 mmol) was
obtained 93 mg (0.45 mmol, 90%) of 17a , Rf 0.38 (10% EtOAc/
hexanes), as a white crystalline solid, mp 50-53 °C, after
chromatography on silica gel 60 (240-400 mesh) eluted with
10% Et2O/pentane. Spectral data appear in the Supporting
Information.
(1S,4S,12S)-4-Meth ylbicyclo[10.1.0]tr idecan -2-on e (17b).
From CuI (93 mg, 0.50 mmol), methyllithium (2.0 mL of a 0.4
M solution, 0.80 mmol), and enone Z-4 (19 mg, 0.10 mmol)
was obtained 18 mg (0.090 mmol, 86%) of 17b, Rf 0.37 (10%
EtOAc/hexanes), as a colorless solid after chromatography on
silica gel 60 (70-230 mesh) eluted with 3% Et2O/hexanes.
Spectral data appear in the Supporting Information.
(1S,4R,12S)-4-P h en ylbicyclo[10.1.0]tr idecan -2-on e (18a).
From CuI (149 mg, 0.78 mmol), phenyllithium (1.1 mL of a
1.4 M solution, 1.5 mmol), and enone E-4 (72 mg, 0.37 mmol)
was obtained 34 mg (0.12 mmol, 33%) of 18a as a white
crystalline solid, mp 86-89 °C, Rf 0.38 (10% EtOAc/hexanes),
and 33 mg (0.11 mmol, 31%) of 18a contaminated with traces
of E-4 after chromatography on silica gel 60 (70-230 mesh)
eluted with 4% EtOAc/hexanes. Spectral data appear in the
Supporting Information.
(1S,4R,15S)-4-Met h ylb icyclo[13.1.0]h exa d eca n -2-on e
(19a ) a n d (1S,4S,15S)-4-Meth ylbicyclo[13.1.0]h exa d eca n -
2-on e (19b). From CuI (202 mg, 1.1 mmol), methyllithium
(5.0 mL of a 0.4 M solution, 2.0 mmol), and enone E-5 (103
mg, 0.44 mmol) were obtained 66 mg (0.26 mmol, 60%) of 19a ,
Rf 0.43 (10% EtOAc/hexanes), mp 59-61 °C, and 43 mg (0.17
mmol, 39%) of 19b, Rf 0.50, mp 51-53 °C, after chromatog-
raphy on silica gel 60 (70-230 mesh) eluted with 3% Et2O/
hexanes. Spectral data appear in the Supporting Information.
(R)-3-Meth ylcyclon on a n on e (20) a n d (3R,7R)-3,7-Dim -
eth ylcycloocta n on e (21). To a solution of Li (11 mg, 1.5
mmol) in NH3 (1 mL) at -78 °C was added a solution of ketone
15a (37 mg, 0.24 mmol) and t-BuOH (36 mg, 0.49 mmol) in
ether (1 mL) via cannula. After 45 min, solid NH4Cl (150 mg,
2.8 mmol) and ether (10 mL) were added, and the reaction
mixture was allowed to attain room temperature. The result-
ing solution was dried (MgSO4) and filtered, and volatiles were
removed. The residue (41 mg) was dissolved in CH2Cl2 (1 mL),
and pyridinium dichromate (91 mg, 0.24 mmol) was added.
After being stirred at room temperature for 12 h, the reaction
mixture was filtered through a plug of silica gel eluted with
ether. Volatiles were removed, and the residual oil was
chromatographed on silica gel 60 (70-230 mesh, 25 g) eluted
with 5% Et2O/pentane to give 27 mg (0.18 mmol, 72%) of 20,
Rf 0.30 (10% EtOAc/hexanes), as a colorless oil contaminated
with <5% of 21.
(1S,3R,5R,13S)-Tr icyclo[11.1.0.03,5]t et r a d eca n -2-on e
(13a ) a n d (1S,3S,5S,13S)-Tr icyclo[11.1.0.03,5]tetr a d eca n -
2-on e (13b). Pentane-washed NaH (25 mg, 80% in oil, 0.83
mmol) was suspended in DMSO (1 mL) at rt, and trimethy-
loxosulfonium iodide (170 mg, 0.63 mmol) was added. After
30 min, a solution of enone Z-4 (103 mg, 0.54 mmol) in DMSO
(1 mL) was added via cannula while maintaining rt by means
of a water bath. After 15 min the reaction was quenched with
water (15 mL) and the reaction mixture was extracted with
pentane. The organic extracts were dried (MgSO4) and
filtered, and volatiles were removed. The residue was chro-
matographed on silica gel (240-400 mesh, 30 g) eluted with
10% Et2O/pentane to give 42 mg (0.20 mmol, 38%) of 13a , Rf
0.36 (10% EtOAc/hexanes), mp 76-80 °C, and 36 mg (0.17
mmol, 33%) of 13b, Rf 0.24, mp 54-58 °C.
Sp ectr a l d a ta for 13a : [R]24 -0.1 (c 2.12, CHCl3); IR
D
(neat) cm-1 1669; 1H NMR δ 0.62-0.80 (4, m), 1.07-1.78 (14,
m), 2.02-2.18 (4, m); 13C NMR δ 15.8, 28.0, 28.3, 29.5, 30.3,
30.5, 33.8, 209.8; HRMS (EI) calcd for C14H22O 206.1671, found
206.1661.
Sp ectr a l d a ta for 13b: [R]24 -78.0 (c 1.68, CHCl3); IR
D
(neat) cm-1 1661; 1H NMR δ 0.75-0.93 (4, m), 1.33-1.60 (16,
m), 1.85-2.00 (2, m); 13C NMR δ 15.2, 24.8, 25.0, 25.9, 26.8,
28.4, 32.3, 208.9.
(1S,3R,5R,16S)-Tr icyclo[14.1.0.03,5]h ep t a d eca n -2-on e
(14a ) a n d (1S,3S,5S,16S)-Tr icyclo[14.1.0.03,5]h ep ta d eca n -
2-on e (14b). From NaH (18 mg, 80% in oil, 0.60 mmol),
trimethyloxosulfonium iodide (126 mg, 0.47 mmol), and enone
Z-5 (91 mg, 0.34 mmol) were obtained 78 mg (0.31 mmol, 81%)
of 14a , Rf 0.42 (10% EtOAc/hexanes), mp 68-70 °C, and 5 mg
(0.02 mmol, 5%) of 14b, Rf 0.29 after chromatography on silica
gel (70-230 mesh, 110 g) eluted with 3-10% EtOAc/hexanes.
Spectral data appear in the Supporting Information.
(1R,4R,8S)-4-Meth ylbicyclo[6.1.0]n on an -2-on e (15a). To
a slurry of CuI (140 mg, 0.76 mmol) in ether (2 mL) at 0 °C
was added methyllithium (1.0 mL of a 1.4 M solution, 1.4
mmol) via syringe. After the solution was stirred for 15 min,
a solution of the enone Z-3 (48 mg, 0.35 mmol) in ether (2 mL)
was added. After an additional 20 min of stirring, the reaction
was quenched by addition of a saturated NaHCO3 solution (5
mL). The mixture was diluted with water (5 mL) and
extracted with ether. The organic extracts were dried (MgSO4)
and filtered, and volatiles were removed. The residue was
chromatographed on silica gel 60 (240-400 mesh, 20 g) eluted
with 10% Et2O/pentane to give 45 mg (0.30 mmol, 84%) of 15a ,
Rf 0.31 (10% EtOAc/hexanes), as a colorless oil.
Sp ectr a l d a ta for 20: 1H NMR δ 1.00 (3, d, J ) 6.5 Hz),
1.23-1.66 (8, m), 1.78-1.89 (2, m), 2.27 (2, ddm, J ) 13.2, 2.4
Hz), 2.35-2.49 (3, m); 13C NMR δ 23.4, 24.1, 24.4, 26.2, 26.3,
31.0, 35.6, 43.6, 51.8, 217.3.
(R)-3-Meth ylcyclotr id eca n on e (22a ) a n d (3R,11R)-3,-
11-Dim eth ylcyclod od eca n on e (23). From Li (28 mg, 4.0
mmol), ketone 17a (89 mg, 0.43 mmol), and t-BuOH (63 mg,
(21) The author has deposited atomic coordinates for 16a with the
Cambridge Crystallographic Data Centre. The coordinates can be
obtained, on request, from the Director, Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge, CB2 1EZ, U.K.
Sp ectr a l d a ta for 15a : [R]23 +136 (c 2.11, CHCl3); IR
D
(neat) cm-1 1689; H NMR δ 0.57-0.83 (2, m), 1.00-1.28 (5,
1