3
932 J . Org. Chem., Vol. 65, No. 13, 2000
Krasutsky et al.
The residue was separated on a silica column: 0.283 g (54%)
oxaadamantane 2 was eluted with hexanes-ether (95:5); 0.007
g (1%) formate 17, 0.234 g (40%) of 2-oxa-exo-adamantan-4-ol
was obtained as a colorless oil. IR (film
,
cm -1): 2980-2960,
1
1781, 1735. H NMR (CDCl ): δ 5.31 (q, 1H, J ) 6.3 Hz), 5.12
3
(q, 1H, J ) 6.3 Hz), 2.28 (m, 2H), 2.2-1.9 (m, 9H), 1.82 (m,
1
3
(
3), and 0.03 g (5%) of lactone 5 were eluted with hexanes-
2H), 1.2 (m, 2H). C NMR (CDCl
J
3
): δ 172.1 (CdO), 156.8 (q,
CF ) 41.0 Hz), 114.4 (q, J CF ) 284.2 Hz), 74.7, 69.8, 33.7,
33.6, 27.2, 24.1, 21.4. MS m/z (rel intensity): 191 (0.5), 180
0.2), 138 (13), 120 (10), 69 (12), 43 (100). Anal. Calcd for
: C, 53.06; H, 5.82. Found: C, 52.98; H, 5.84.
en d o-7-Acetoxybicyclo[3.3.1]n on -2-en e (18). A solution
2
1
ether (1:1).
-Ad a m a n ta n yl F or m a te (17).38 (a ) The solution of TF-
2
(
PAA in TFAA (0.523 g, 1.81 mmol TFPAA) was added dropwise
over 4 h to a stirred solution of 5 (0.158 g, 0.602 mmol) in
13 17 3 4
C H F O
TFAA (1.5 mL) at room temperature, and then CH
was added. The mixture was then washed with H
aqueous Na SO and dried over Na SO . The residue after
2
Cl
2
(15 mL)
2
O and 5%
of 5-methyl-4,6-dioxabishomoadamant-5-yl cation (21) pre-
pared from alcohol 1 (0.3 g, 1.8 mmol) in TFPAA and TFAA
2
3
2
4
solvent evaporation was purified on a silica column (10% ether
in hexane). Formate 17 (0.095 g, 88%) was obtained. (b) The
solution of 2-methyleneadamantane (14) (0.184 g, 1.24 mmol)
was added dropwise to a well-stirred suspension of dry Na
2
-
HPO (25.6 g 180 mmol) in dry CH Cl (200 mL) for 10 min at
4
2
2
-25 °C and then stirred for 0.5 h more at this temperature.
Dimethyl sulfide (3.35 g, 54 mmol) was added to the reaction
mixture and stirred for 20 min at -25 °C. The temperature
was then increased to room temperature and the reaction
stirred for an additional 20 min. The reaction mixture was
2 2
in 0.5 mL of CH Cl was added dropwise over 10 min at room
temperature to the solution of TFPAA in TFAA (1 g, 3.73 mmol
TFPAA) and was stirred for 0.5 h. Using the same purification
procedure as in (a ) formate 17 (0.203 g, 91% yield) was
obtained. (c) A solution of oxirane 15 (0.2 g, 1.24 mmol) in 0.5
washed with water and dried over Na
evaporation of CH Cl was purified on a silica column with
ether-hexane (1:4), and olefin 18 (0.283 g, 87%) was obtained.
2 4
SO . The residue after
mL of CH
2
Cl
2
was added dropwise over 10 min at room
2
2
temperature to the solution of TFPAA in TFAA (1 g, 3.73 mmol
TFPAA) and was stirred for 0.5 h. Using the same purification
procedure as in (a ), formate 17 (0.21 g, 94% yield) was
-
1
1
IR (film, cm ): 3010-2960, 1726, 1624. H NMR (CDCl
5.82 (m, 1H), 5.65 (dt, J ) 9.9 Hz, J ) 3.6 Hz, 1H), 5.01 (m,
1H), 2.44-2.23 (m, 2H), 2.17 (m, 1H), 2.07-1.81 (m, 7H), 1.74
(m, 2H), 1.56 (m, 1H). 13C NMR (CDCl
): 170.7 (CdO), 131.3,
27.2, 68.9, 36.8, 33.4, 32.4, 30.8, 27.1, 25.3, 21.4. MS m/z (rel
3
): δ
1
2
+
obtained. MS m/z (rel intensity): 180 (M , 1.5), 134 (100), 92
(
63), 79 (18), 67 (6).
-Meth yl-4,6-d ioxa bish om oa d a m a n t-5-yl Ca tion (21).
a ) Alcohol 1 (0.3 g, 1.8 mmol) was added at -25 °C to a
3
1
5
+
intensity): 180 (M , 1.0), 130 (0.9), 120 (20), 79 (100), 43 (28).
(
Anal. Calcd for C11
H, 8.87.
16 2
H O : C, 73.30; H, 8.95. Found: C, 72,96;
solution of TFPAA in TFAA (9.8 g, 36.1 mmol TFPAA). After
being stirred for 2 h at -25 °C, cation 21 was formed in the
reaction mixture. The formation of 25 was monitored by the
Acetyltr iflu or oa cetyl P er oxid e. Trifluoroacetic anhy-
dride (10 g, 47.6 mmol) was added to acetic acid (2.85 g, 47.5
mmol) at 20 °C and stirred for 0.5 h. The temperature was
then decreased to 0 °C, and a solution of TFPAA in TFAA (12.9
g, 47.6 mmol) was added dropwise. The reaction mixture was
stirred for 0.5 h, and the concentration of acetyltrifluoroacetyl
1
H NMR spectra of reaction mixture at -25 °C. (b) A solution
of trifluoroacetate 5 (0.3 g, 1.1 mmol) in TFAA (0.3 mL) was
added at -25 °C to a solution of TFPAA in TFAA (6.17 g, 22.8
mmol TFPAA). After the mixture was stirred for 1 h 20 min
at -25 °C, cation 21 was formed in the reaction. The formation
1
19
19
of 21 was monitored by the H NMR spectra of the reaction
peroxide was checked by F NMR. F NMR (CDCl
(s, CF , acetyltrifluoroacetyl peroxide), -76.2 (s, CF
H NMR (CDCl ): δ 2.3 (s, CH ).
2-Oxa -exo-a d a m a n ta n -4-ol (3). (a ) Dry Na HPO (6.4 g,
3
): δ -71.8
3
1
mixture at -25 °C. H NMR (CF
3
COOH): δ 5.2 (t, 2H, J )
) 17.4 Hz, J ) 6.2 Hz),
COOH): δ 181.2,
3
, TFAA).
1
6
1
8
.2 Hz), δ 2.0 (s, 3H), 1.8 (dt, 4H, J
1
2
3
3
1
3
39
.5-1.7 (m, 6H), 1.1 (s, 2H). C NMR (CF
3
2
4
9.6, 33.1, 28.4, 22.9, 19.1.
45 mmol) was added to a dry CH Cl2 (50 mL) solution of
2
Acid ic Hyd r olysis of 5-Meth yl-4,6-d ioxa bish om oa d a -
TFPAA in TFAA (2.4 g, 8.9 mmol TFPAA) at 0 °C. After 0.5 h
of stirring, a CH Cl (0.3 mL) solution of olefin 18 (0.2 g, 1.1
2 2
mmol) was added and stirred for another 0.5 h. The reaction
m a n tyl Ca tion (21). A reaction mixture from the previous
experiment (0.3 g of 1, 1.8 mmol) was added dropwise over 10
min at 0 °C to a 10% solution of TFAA (100 mL). The solution
mixture was then washed with water and 5% aqueous Na
SO solution and dried over anhydrous Na SO and the CH
Cl
2
-
-
was extracted with CH
organic extracts were washed with water and dried over Na
SO . The residue after solvent evaporation was purified on a
2
Cl
2
(4 × 10 mL), and the combined
3
2
4
2
-
2
evaporated. The residue was purified on a silica column
2
(ether/hexane 1:1), and alcohol 3 (0.16 g, 94%) was obtained.
(b) A solution of 5-methyl-4,6-dioxabishomoadamant-5-yl cat-
ion (21) prepared from alcohol 1 (0.3 g, 1.8 mmol) in TFPAA,
and TFAA was added dropwise to a well stirred suspension of
4
silica column with ether-hexane (1:1). En d o,en d o-3-h y-
d r oxy-7-a cetoxybicyclo[3.3.1]n on a n e (27) (0.292 g, 82%)
was obtained as white crystals, mp 81-82 °C. IR (Film, cm
-
1
1
)
: 3390, 2990-2960, 1724. H NMR (CDCl
) 7.5 Hz, J ) 6.3 Hz), 1.6-2.2
m, 14H), 1.52 (m, 1H). 13C NMR (CDCl
): δ 170.4 (CdO), 69.6,
5.9, 36.8, 36.2, 27.7, 24.6, 21.5. MS m/z (rel intensity) 154
3
): δ 5.06 (q, 1H,
2 4 2 2
dry Na HPO (25.6 g 180 mmol) in dry CH Cl (200 mL) for
J ) 5.4 Hz), δ 4.01 (tt, 1H, J
1
2
10 min at -25 °C and then stirred for 0.5 h at this tempera-
ture. The temperature was then increased to room tempera-
ture and stirred for additional 0.5 h. The reaction mixture was
(
6
(
C
3
0.26), 138 (37), 120 (38), 79 (100), 43 (47). Anal. Calcd for
: C, 66.64; H, 9.15. Found: C, 66.52; H, 9.02. X-ray
washed with H
dried over anhydrous Na
of CH Cl was purified on a silica column with ether-hexane
2
O and 5% aqueous Na
2 3
SO solution and then
H
24
O
2
2
SO . The residue after evaporation
4
14
quality single crystals for 27 were obtained by slowly crystal-
lizing a solution of 27 in hexane. Crystal data for 27 (173 K,
MoKR-radiation, Siemens SMART Platform CCD diffractome-
2
2
(1:1) and alcohol 3 (0.248 g, 89%) was obtained. Mp: 267-269
°C (lit.39 mp 268-273 °C). MS m/z (rel intensity): 154 (M ,
100), 136 (9), 110 (79).
+
ter): C11
H
18
O
3
, FW ) 198.25, a ) 12.3109(7) Å, b ) 19.4314-
11) Å, c ) 8.9908(5) Å, â ) 97.973(2)°, monoclinic, P2 /c, Z )
) 1.236 g/cm . R factor ) 0.0706 for
179 independent observed reflection (I>2σ(I)); weighted R2
2-Oxa a d a m a n ta n e (2).18,26,39 (a ) Hydroxyacetate 27 (0.1 g,
0.5 mmol) was added to the 95% sulfuric acid (65 g) at 0 °C,
and the reaction was stirred for 0.5 h and then poured into
H O and extracted with CH Cl (4 × 10 mL). The combined
(
8
2
1
3
3
, V ) 2130.0(2) Å , D
c
factor ) 0.1226. Selected bond lengths and bond angles of
structure 27 are listed in Figure 2. Further details on crystal
structure of 27 are available in the Supporting Information.
2
2
2
organic extracts were washed with 5% aqueous NaHCO and
3
dried over anhydrous Na SO . After removal of the solvent,
2
4
en d o,en d o-3-Acetoxy-7-tr iflu or oa cetoxybicyclo[3.3.1]-
n on a n e (28). Alcohol 27 (0.1 g, 0.5 mmol) was added to
TFAAn (2 g, 9.5 mmol) at 0 °C. After being stirred for 0.5 h,
the reaction mixture was evaporated and purified on a silica
column (40% ether/hexane). Trifluoroacetate 28 (0.144 g, 98%)
oxaadamanatne 2 (0.067 g, 96%) was obtained. (b) Olefin 18
(0.2 g, 1.1 mmol) was added to 95% sulfuric acid (120 g) at 0
°C, and the reaction was stirred for 0.5 h and then poured into
H
2
O and extracted with CH
organic extracts were washed with 5% aqueous NaHCO
dried over anhydrous Na SO . After removal of the solvent,
2
Cl
2
(4 × 10 mL). The combined
3
and
2
4
(
38) Isaev, S. D.; Shrstyuk, V. P.; Kozlov, O. F.; Skripnik, V. V.;
Yanku, I. Teor. Eksp. Khim. 1991, 27, 211.
(39) Subramaniam, R.; Fort, R. C., J r. J . Org. Chem. 1984, 49, 2891.