Route to Closely Related Cyclopropane Stereoisomers
J . Org. Chem., Vol. 66, No. 24, 2001 7965
(
(
2
7
1
dd, J ) 6.0, 5.4 Hz, 1H), 3.46 (dd, J ) 18.0, 7.7 Hz, 1H), 3.51
dd, J ) 18.0, 6.9 Hz, 1H), 7.15-7.30 (m, 5H), 7.46-7.47 (m,
(2:98, ethyl acetate/benzene); IR 1715, 1687, 1394, 1178, 1058
-
1 1
cm ; H NMR (CDCl , 600 MHz) δ 0.91 (ddd, J ) 7.0, 5.2, 4.6
3
H), 7.53-7.56 (m, 1H), 7.96-7.98 (m, 2H); 13C NMR (CDCl
,
Hz, 1H), 1.11 (ddd, J ) 8.2, 8.1, 4.6 Hz, 1H), 1.60-1.63 (m,
6H), 1.65 (ddddd, J ) 8.8, 8.2, 7.1, 7.0, 6.3, 1H), 1.76 (ddd, J
) 8.8, 8.1, 5.2 Hz, 1H), 2.03-2.07 (m, 6H), 2.10 (brs, 3H), 3.28
3
5 MHz) δ 25.0, 29.2, 30.7, 30.9, 36.1, 36.2, 41.2, 80.9, 125.6,
26.3, 128.0, 128.3, 128.4, 128.5, 133.0, 140.0, 170.9, 199.0;
+
MS m/z (%): 414 (M , 3), 279 (50), 262 (45), 135 (100); HRMS
(dd, J ) 18.1, 7.1 Hz, 1H), 3.33 (dd, J ) 18.1, 6.3 Hz, 1H),
1
13
of 8 (X ) Y ) Ph, R ) 1-Ad) (C22
14.2182.
tr a n s-(()-ter t-Bu tyl 2-(2-Ben zoylcyclop r op yl)a ceta te
H
30
O
3
) calcd, 414.2194; found,
7.41-7.47 (m, 2H), 7.50-7.58 (m, 1H), 7.93-7.97 (m, 2H); C
4
3
NMR (CDCl , 150 MHz) δ 13.0, 15.8, 18.7, 30.7, 36.1, 36.5,
41.3, 80.5, 128.0, 128.5, 132.9, 137.0, 172.2, 199.6; MS m/z
1
+
(
5, X ) P h , Y) H, R ) t-Bu ). R
f
0.60 (4:1 hexane/ethyl
(%): 339 (M + H, 20), 135 (100); HRMS of 8 (X ) Ph, Y) H,
1
acetate); mp 28-30 °C (heptane); IR (neat) 1730, 1668, 1599,
R ) 1-Ad) (C22
27 3
H O ) calcd, 339.1960; found, 339.1953.
-
1
1
1
6
1
579 cm ; H NMR (CDCl
3
, 600 MHz) δ 0.98 (ddd, J ) 8.1,
tr a n s-(()-Ben zyl 2-(2-Oxo-2-ph en yleth yl)cyclopr opan e-
1-ca r boxyla te (7, X ) P h , Y ) H, R1 ) Bn ). R
0.25 (1:9,
ethyl acetate/hexane); mp ) 82.5-83.5 °C (ether/pentane); IR
.4, 4.1 Hz, 1H), 1.40 (s, 9H), 1.55 (ddd, J ) 8.8, 4.8, 4.1 Hz,
H), 1.85 (ddddd, J ) 8.8, 7.8, 6.4, 6.4, 4.8 Hz, 1H), 2.24 (dd,
f
-
1
1
J ) 15.4, 7.8 Hz, 1H), 2.46 (dd, J ) 15.4, 6.4 Hz, 1H), 2.58
(
3
1724, 1683, 1267, 1025 cm ; H NMR (CDCl , 300 MHz) δ
ddd, J ) 8.1, 4.8, 4.8 Hz, 1H), 7.45-7.48 (m, 2H), 7.54-7.57
0.86 (ddd, J ) 8.8, 8.2, 4.5 1H), 1.37 (ddd, J ) 8.7, 4.5, 4.5 Hz,
1H), 1.58 (ddd, J ) 8.8, 4.5, 4.5 Hz), 1.89 (ddddd, J ) 8.7, 8.2,
7.2, 6.6, 4.5, 1H), 2.89 (dd, J ) 16.8, 7.2 Hz, 1H), 3.10 (dd, J
1
3
(m, 1H), 7.99-8.01 (m, 2H); C NMR (CDCl
3
, 150 MHz) δ 17.5,
2
1
7
7
2.0, 24.3, 28.0, 39.5, 80.7, 128.0, 128.4, 132.7, 137.9, 171.0,
+
99.3; MS m/z (%): 260 (M , 0.1), 205 (100), 187 (26), 105 (83),
) 16.8, 6.6 Hz), 5.12 and 5.14 (AB
q
, J ) 12.3 Hz, 2H), 7.3-7.6
, 75 MHz) δ 15.1,
7 (11), 57 (53). Anal. Calcd for C16
.74. Found: C, 73.50; H, 7.13.
H
2
O
3
(260.3): C, 73.82; H,
(m, 6H), 7.9-7.95 (m, 2H); 13C NMR (CDCl
3
17.8, 20.0, 41.9, 66.3, 128.0, 128.12, 128.14, 128.5, 128.6,133.2,
133.0, 136.5, 173.5, 198.0; MS m/z (%): 294 (M , 5) 188 (10),
+
tr a n s-(()-ter t-Bu tyl 2-(2-Oxo-2-p h en yleth yl)cyclop r o-
1
p a n e-1-ca r boxyla te (7, X ) P h , Y) H, R ) t-Bu ). R
(
1
J ) 8.3, 6.3, 4.5 Hz, 1H), 1.24 (ddd, J ) 9.0, 4.5, 4.5 Hz, 1H),
1
1
Hz, 1H), 7.45-7.47 (m, 2H), 7.55-7.58 (m, 1H), 7.92-7.93 (m,
2
8
f
0.50
105 (100). Anal. Calcd for C19
C, 77.68; H, 6.08.
18 3
H O : C, 77.53; H, 6.16; Found:
4:1 hexane/ethyl acetate); mp 71-72 °C (heptane); IR 1720,
-1 1
683, 1595, 1578 cm ; H NMR (CDCl
3
, 600 MHz) δ 0.75 (ddd,
cis-(()-Ben zyl 2-(2-Oxo-2-p h en yleth yl)cyclop r op a n e-
1
1-ca r boxyla te (8, X ) P h , Y ) H, R ) Bn ). R
f
0.4 (benzene);
-
1 1
.38-1.46 (m, 10H), 1.76 (ddddd, J ) 9.0, 7.5, 6.3, 6.1, 4.1 Hz,
H), 2.82 (dd, J ) 16.8, 7.5 Hz, 1H), 3.12 (dd, J ) 16.8, 6.1
IR (neat) 1727, 1687, 1451, 1401, 1162 cm ; H NMR (CDCl
3
,
300 MHz) δ 1.03 (ddd, J ) 7.2, 5.2, 4.9 Hz, 1H), 1.23 (ddd, J
) 8.1, 8.1, 4.9 Hz, 1H), 1.77 (ddddd, J ) 8.4, 8.1, 7.2, 7.0, 6.8,
1H), 1.95 (ddd, J ) 8.4, 8.1, 5.2 Hz, 1H), 3.28 (dd, J ) 20.0,
6.8 Hz, 1H), 3.34 (dd, J ) 20.0, 7.0 Hz, 1H), 5.05 and 5.12
1
3
H); C NMR (CDCl
3
, 150 MHz) δ 14.9, 17.4, 21.4, 28.3, 42.3,
0.5, 128.3, 128.9, 133.3, 136.9, 173.1, 198.6; MS m/z (%): 260
+
(M , 9), 204 (10), 187 (29), 105 (100), 77 (21), 57 (8). Anal. Calcd
(AB
q
, J ) 12.0 Hz, 2H), 7.2-7.6 (m, 6H), 7.90-7.94 (2H, m);
1
3
for C16 (260.3): C, 73.82; H, 7.74. Found: C, 73.97; H,
7
H
2
O
3
C NMR (CDCl
3
, 75 MHz) δ 13.77, 16.5, 17.7, 36.5, 66.3,
.58.
cis-(()-ter t-Bu tyl 2-(2-Oxo-2-ph en yleth yl)cyclopr opan e-
128.02, 128.08, 128.1, 128.4, 128.5, 132.9, 136.1, 136.8, 173.1,
199.2; MS m/z (%): 295 (M , 15), 188 (18), 105 (100), HRMS
of 8 (X ) Ph, Y ) H, R ) Bn) C19
found: 295.1344.
+
1
1
1
-ca r boxyla te (5, X ) P h , Y) H, R ) t-Bu ). R
f
0.65 (4:1
H
18
O
3
(+H): calcd, 295.1334;
hexane/ethyl acetate); mp 51-53 °C (heptane); IR 1714, 1687,
1
7
(
(
-
1 1
594, 1577 cm ; H NMR (CDCl
3
, 600 MHz) δ 0.93 (ddd, J )
tr a n s-(()-t-Bu t yl 2-Met h yl-3-(2-oxo-2-p h en ylet h yl)-1-
1
.2, 5.4, 4.8 Hz, 1H), 1.12 (ddd, J ) 8.7, 8.1, 4.8 Hz, 1H), 1.38
cyclop r op a n eca r boxyla te (7, X ) P h , Y) Me, R ) t-Bu ).
s, 9H), 1.67 (ddddd, J ) 8.7, 8.7, 7.5, 7.2, 6.4 Hz, 1H), 1.82,
ddd, J ) 8.7, 8.1, 5.4 Hz, 1H), 3.29 (dd, J ) 18.0, 7.5 Hz, 1H),
R 0.25 (9:1 hexane/ethyl acetate); mp 47-49 °C (heptane); IR
f
-
1 1
1715, 1690, 1598, 1581 cm ; H NMR (CDCl , 600 MHz) δ
3
3
.34 (dd, J ) 18.0, 6.4 Hz, 1H), 7.43-7.46 (m, 2H), 7.53-7.56
1.16 (ddq, J ) 9.0, 6.0, 5.4 Hz, 1H), 1.23 (d, J ) 6.0 Hz, 3H),
1.45 (s, 9H), 1.50 (dd, J ) 9.0, 5.4 Hz, 1H), 1.62 (dddd, J )
7.8, 6.0, 5.4, 5.4 Hz, 1H), 2.75 (dd, J ) 16.8, 7.8 Hz, 1H), 3.17
(dd, J ) 16.8, 6.0 Hz, 1H), 7.45-7.47 (m, 2H), 7.55-7.57 (m,
1
3
(m, 1H), 7.93-7.95 (m, 1H); C NMR (CDCl
3
, 150 MHz) δ 13.0,
1
1
7
7
5.9, 18.8, 28.1, 36.6, 80.4, 128.0, 128.5, 132.9, 137.0, 172.4,
99.5; MS m/z (%): 260 (M , 2), 205 (40), 187 (100), 105 (35),
+
7 (12), 57 (15). Anal. Calcd for C16
.74. Found: C, 74.12; H, 7.83.
H
2
O
3
(260.3): C, 73.82; H,
1H), 7.91-7.93 (m, 2H); 13C NMR (CDCl
, 150 MHz) δ 11.7,
3
22.8, 22.8, 26.6, 28.2, 42.1, 80.3, 128.1, 128.7, 133.1, 136.8,
+
tr a n s-(()-1-Ad a m a n tyl 2-(2-Ben zoylcyclop r op yl)a ce-
171.3, 198.8; MS m/z (%): 274 (M , 2), 219 (21), 201 (100),
1
ta te (5, X ) P h , Y) H, R ) 1-Ad ). R
benzene); IR (neat) 1727, 1668, 1598, 1450, 1402, 1223, 1180,
1
6
1
(
6
(
f
0.50 (2:98, ethyl acetate/
105 (52), 77 (19), 57 (32). Anal. Calcd for C17
74.42; H, 8.08. Found: C, 74.87; H, 8.02.
22 3
H O (274.4): C,
-
1
1
056 cm ; H NMR (CDCl
3
, 600 MHz) δ 0.98 (ddd, J ) 8.0,
tr a n s-(()-ter t-Bu tyl 2-(2-Oxop en tyl)-3-p r op yl-1-cyclo-
.4, 4.0 Hz, 1H), 1.56 (ddd, J ) 8.8, 4.8, 4.0 Hz, 1H), 1.61-
p r op a n eca r boxyla te (7, X ) Y ) P r , R1 ) t-Bu ). R
f
0.4 (9:
-
1 1
.63 (m, 6H), 1.84 (ddddd, J ) 8.8, 7.8, 6.4, 6.4, 4.0, 1H), 2.03
1, hexane/ethyl acetate); IR (neat) 1716, 1367, 1155 cm ; H
NMR (CDCl
brs, 3H), 2.22 (dd, J ) 15.3, 7.8 Hz, 1H), 2.46 (dd, J ) 15.3,
3
, 600 MHz) δ 0.89 (t, J ) 6.6 Hz, 3H), 0.91 (t, J
.4 Hz, 1H), 2.57 (ddd, J ) 8.0, 4.8, 4.0 Hz, 1H), 7.45-7.46
) 7.2 Hz, 3H), 1.05 (m, 1H), 1.45-1.65 (m, 9H), 1.44 (s, 9H),
1
3
m, 2H), 7.55-7.56 (m, 1H), 7.99-8.00 (m, 2H); C NMR
2.22 (dd, J ) 16.2, 7.8 Hz, 1H), 2.41 (dd, J ) 7.2, 7.2 Hz, 2H),
(
1
CDCl , 50 MHz) δ 17.5, 22.2, 24.4, 30.8, 36.1, 39.6, 41.3, 80.8,
3
2.46 (dd, J ) 16.2, 6.6 Hz, 1H); 13C NMR (CDCl
, 150 MHz) δ
3
+
28.0, 128.4, 132.7, 137.9, 170.8, 199.3; MS m/z (%): 339 (M
13.7, 13.7, 17.0, 21.9, 22.6, 26.0, 28.1, 28.7, 28.7, 44.1, 46.4,
+
+
7
H, 30), 135 (100). Anal. Calcd for C22
H
26
O
3
: C, 78.07; H,
80.2, 171.3, 209.5; MS m/z (%): 268 (M , 21), 211 (40), 196
1
.74; Found: C, 78.11; H, 7.86.
tr a n s-(()-1-Ad a m a n tyl 2-(2-Oxo-2-p h en yleth yl)cyclo-
(100); HRMS of 7 (X ) Y ) Pr, R ) t-Bu): calcd, C16
28 3
H O
(+H): 269.2117; found: 269.2113.
1
p r op a n e-1-ca r boxyla te (7, X ) P h , Y) H, R ) 1-Ad ). R
.37 (2:98, ethyl acetate/benzene); mp ) 101-102 °C (dichlo-
f
cis-(()-ter t-Bu tyl 2-(2-Oxop en tyl)-3-p r op yl-1-cyclop r o-
0.6 (9:1,
0
p a n eca r boxyla te (8, X ) Y ) P r , R1 ) t-Bu ). R
hexane/ethyl acetate); IR (neat) 1716, 1457, 1366, 1154 cm
f
-
1
1
-1
romethane/hexane); IR 1714, 1685, 1268, 1085, 1058 cm ; H
NMR (CDCl
;
1
3
, 600 MHz) δ 0.76 (ddd, J ) 8.6, 6.3, 4.5, 1H) 1.24
ddd, J ) 8.8, 4.6, 4.5, 1H), 1.42 (ddd, J ) 8.6, 4.6, 4.3 Hz,
H NMR (CDCl
3
, 600 MHz) δ 0.89 (t, J ) 7.5 Hz, 3H), 0.90 (t,
(
J ) 7.2 Hz, 3H), 1.2-1.63 (m, 10H), 1.44 (s, 9H), 2.35 (t, J )
1
2
3
(
3
H), 1.65 (brs, 6H), 1.76 (ddddd, J ) 8.8, 7.2, 6.3, 6.0, 4.3, 1H),
.11 (brs, 6H), 2.16 (brs, 3H), 2.80 (dd, J ) 16.8, 7.2 Hz, 1H),
.19 (dd, J ) 16.8, 6.0 Hz, 1H), 7.40-7.60 (m, 3H), 7.94-7.95
7.5 Hz, 2H), 2.66-2.82 (m, 2H); 13C NMR (CDCl
, 150 MHz) δ
3
13.7, 13.7, 17.2, 21.9, 23.0, 25.5, 27.2, 28.1, 34.9, 40.3, 44.5,
+
80.1, 172.3, 210.3; MS m/z (%): 269 (M + H, 30), 213 (52),
1
3
1
m, 2H); C NMR (CDCl
3
, 75 MHz) δ 14.7, 17.2, 21.1, 30.7,
195 (100); HRMS of 8 (X ) Y ) Pr, R ) t-Bu): calcd, C16
(+H): 269.2117; found: 269.2113.
28 3
H O
6.1, 41.3, 42.0, 80.4, 128.0, 128.6, 133.1, 136.5, 172.6, 198.4;
+
MS m/z (%): 338 (M , 25), 203 (45), 135 (100). Anal. Calcd for
: C, 78.07; H, 7.74; Found: C, 78.27; H, 7.83.
cis-(()-1-Ad a m a n tyl 2-(2-Oxo-2-p h en yleth yl)cyclop r o-
p a n e-1-ca r boxyla te (8, X ) P h , Y) H, R1 ) 1-Ad ). R
0.47
tr a n s-(()-P h en yl-2-[2-(ben zyloxy)-2-oxoeth yl]-3-p h en -
22 26 3
C H O
ylcyclop r op a n e-1-ca r boxyla te (19). To a mixture of trans
1
4
(5, X ) Y ) Ph, R ) Bn) (0.35 g, 0.94 mmol) in CH
2 2
Cl (4
f
mL) was added m-CPBA (0.58 g, 0.94 mmol, 70%) and the