M. De Rosa et al. / Tetrahedron: Asymmetry 11 (2000) 3187±3195
3193
1
.66 (s, 6H); ꢀ (100.03 MHz, CDCl ) 167.9, 161.2, 150.3, 147.4, 126.5, 123.8, 106.9, 95.5, 69.8,
C 3
+
25
4
3.1, 25.2, 24.6; m/z (EIMS) 293 (M ); ꢂ =+21 (c 1.2, CHCl ), e.e. 75% (R); HPLC analysis
D
hexanes:isopropanol, 8:2), 0.8 mL/min; (S) enantiomer t =11.29 min; (R) enantiomer t =14.23
3
(
min.
r
r
3
.2.2. 6-(2-Hydroxy-undecyl)-2,2-dimethyl[1,3]dioxin-4-one 3f (entry 10, Table 2)
The product was obtained as a yellow oil. [Found: C, 68.51; H, 10.21; C H O requires: C,
17
30
4
6
1
1
8.42; H, 10.13%]; R (10% Et O/CHCl ) 0.2; ꢁ
(CHCl ) 3500±3250 (bs), 3020, 2931, 2855,
max 3
f
2
3
721, 1637, 1393, 1376; ꢀ (400 MHz, CDCl ) 5.31 (s, 1H), 3.88 (bs, 1H), 2.37 (dd, 1H, J=3.96,
H
3
4.5 Hz), 2.30 (dd, 1H, J=8.4, 14.5 Hz), 1.68 (s, 6H), 1.49±1.24 (m, 16H), 0.86 (t, 3H, J=6.1 Hz);
ꢀC (100.03 MHz, CDCl ) 172.9, 169.4, 161.1, 114.9, 106.6, 95.1, 68.9, 41.7, 37.4, 31.9, 29.5, 29.3,
3
+
25
D
25.5, 25.3, 24.8, 22.7, 14.1; m/z (EIMS) 298 (M ); ꢂ =+13 (c 1.2, CHCl ), e.e. 89% (R); HPLC
analysis (hexanes:isopropanol, 98:2), 0.5 mL/min; (R) enantiomer t =51.56 min; (S) enantiomer
3
r
tr=60.04 min.
3
5
.2.3. 4-[2-Hydroxy-2-(4-methoxy-phenyl)-ethyl]-1,5-dioxa-spiro[5.5]undec-3-en-2-one 4c (entry
, Table 2)
The product was obtained as a yellow oil. [Found: C, 68.03; H, 6.88; C H O requires: C,
22
18
5
6
1
4
2
1
7.91; H, 6.97%]; R (10% Et O/CHCl ) 0.2; ꢁ
(CHCl ) 3437, 3000, 1712, 1633, 1612, 1512,
max 3
f
2
3
382, 1245; ꢀ (400 MHz, CDCl ) 7.25 (d, 2H, J=8.6 Hz), 6.85 (d, 2H, J=8.6 Hz), 5.19 (s, 1H),
H
3
.92±4.88 (m, 1H), 3.77 (s, 3H), 2.65 (dd, 1H, J=8.6, 14.6 Hz), 2.62 (partially superimposed, 1H),
.55 (dd, 1H, J=4.8, 14.6 Hz), 1.96±1.42 (m, 10H); ꢀ (100.03 MHz, CDCl ) 168.4, 161.4, 159.4,
C
3
+
35.1, 127.0, 114.0, 107.3, 95.3, 70.8, 55.3, 43.2, 34.1, 33.3, 24.6, 22.2; m/z (EIMS) 318 (M );
25
ꢂ =+23 (c 1.2, CHCl ), e.e. 95% (R); HPLC analysis (hexanes:isopropanol, 8:2), 0.8 mL/min;
D
S) enantiomer t =12.28 min; (R) enantiomer t =16.56 min.
3
(
r
r
3.2.4. 4-[2-Hydroxy-2-(4-nitro-phenyl)-ethyl]-1,5-dioxa-spiro[5.5]undec-3-en-2-one 4d (entry 7,
Table 2)
The product was obtained as yellow oil. [Found: C, 61.11; H, 5.82; N, 4.33; C H NO
6
17
19
requires: C, 61.25; H, 5.75; N, 4.20%]; R (10% Et O/CHCl ) 0.1; ꢁ
(CHCl ) 3605, 3389, 2946,
3
f
2
3
max
1719, 1641, 1606, 1525, 1385, 1348; ꢀ (400 MHz, CDCl ) 8.21 (d, 2H, J=8.6 Hz), 7.57 (d, 2H,
H 3
J=8.6 Hz), 5.30 (s, 1H), 5.14±5.10 (m, 1H), 3.09 (d, 1H, J=3.7 Hz), 2.67±2.60 (m, 2H), 1.99±1.45
(
m, 10H); ꢀ (100.03 MHz, CDCl ) 167.5, 161.3, 150.2, 147.6, 126.6, 123.9, 107.7, 95.8, 70.1, 43.3,
C 3
+
25
D
3
analysis (hexanes:isopropanol, 8:2), 0.8 mL/min; (S) enantiomer t =16.58 min; (R) enantiomer
4.1, 33.3, 24.5, 22.2; m/z (EIMS) 333 (M ); ꢂ =+26 (c 1.3, CHCl ), e.e. 90% (R); HPLC
3
r
tr=23.36 min.
3
.2.5. 4-(2-Hydroxy-undecyl)-1,5-dioxa-spiro[5.5]undec-3-en-2-one 4f (entry 11, Table 2)
The product was obtained as a yellow oil. [Found: C, 71.13; H, 10.01; C H O requires: C,
20
34
4
7
1
1
0.97; H, 10.12%]; R (10% Et O/CHCl ) 0.3; ꢁ
(CHCl ) 3400±3250 (bs), 3017, 2937, 2861,
max 3
f
2
3
714, 1634, 1380, 1264; ꢀ (400 MHz, CDCl ) 5.28 (s,1H), 3.91 (bs, 1H), 2.42 (dd, 1H, J=8.3,
H
3
4.5 Hz), 2.33 (dd, 1H, J=8.3, 14.5 Hz), 2.00±1.43 (m, 26H), 0.87 (t, 3H, J=5.9 Hz); ꢀ (100.03
C
MHz, CDCl ) 169.0, 161.2, 131.5, 107.2, 95.2, 69.0, 41.7, 37.4, 34.0, 33.5, 31.9, 29.5, 29.3, 25.5,
3
+
25
D
2
analysis (hexanes:isopropanol, 98:2), 0.5 mL/min; (R) enantiomer t =64.20 min; (S) enantiomer
4.6, 22.7, 22.2, 14.1; m/z (EIMS) 338 (M ); ꢂ =+33 (c 1.2, CHCl ), e.e. 36% (R); HPLC
3
r
tr=67.94 min.