J. Shi et al. / Tetrahedron 67 (2011) 1781e1787
1785
20
7.122e7.453 (m, 6H), 4.118 (dd, J1¼4.4 Hz, J2¼14.4 Hz, 1H), 4.001
(dd, J1¼4.0 Hz, J2¼14.4 Hz, 1H), 3.687 (dt, J1¼4.4 Hz, J2¼14.8 Hz, 2H),
2.673 (dt, J1¼4.4 Hz, J2¼7.2 Hz, 2H), 0.675 (s, 3H), 0.645 (s, 3H) ppm;
30.8 mg, 68% yield, 97% ee [
a]
þ2.50 (c¼1.20 in CH2Cl2). HPLC
D
DAICEL CHIRALCEL IA, n-hexane/2-propanol¼80/20, flow
rate¼1.0 mL/min,
l
¼254 nm, retention time: 21.607 min (major),
13C NMR (100 MHz, CDCl3)
d
¼205.5, 167.6, 164.8, 148.0, 143.9, 138.7,
26.160 min (minor). 1H NMR (400 MHz, CDCl3)
d¼8.213 (d, 2H),
135.4, 130.7, 129.7, 129.3, 128.68, 126.8, 124.3, 106.8, 59.8, 49.9,
49.78, 42.2, 42.4, 28.95, 28.4 ppm; HRMS (ESI-TOF) calcd for
C23H20ClNO7 ([MꢁHþ])¼456.0850, Found 456.0847.
6.858e7.447 (m, 6H), 4.105 (dd, J1¼4.4 Hz, J2¼14.8 Hz, 1H), 3.988
(dd, J1¼4.4 Hz, J2¼14.0 Hz, 1H), 3.770 (s, 3H), 3.687 (dt, J1¼5.6 Hz,
J2¼14.4 Hz, 2H), 2.648 (dt, J1¼4.4 Hz, J2¼10.8 Hz, 2H), 0.674 (s, 3H),
0.605 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3)
d
¼206.2, 167.5, 165.2,
4.3.4. 7-(4-Chlorophenyl)-3,3-dimethyl-11-(4-nitrophenyl)-2,4-diox-
aspiro[5.5]undecane-1,5,9-trione (5d). (C23H20ClNO7) a white solid;
159.8, 147.8, 144.2, 129.6, 128.6, 124.1, 114.5, 106.7, 102.9, 60.3, 55.3,
49.9, 43.4, 41.9, 29.7, 28.9, 28.4 ppm; HRMS (ESI-TOF) calcd for
C24H23NO8 ([MꢁHþ])¼452.1345, Found 452.1345.
20
37.1 mg, 81% yield, 83% ee [
a]
ꢁ0.94 (c¼3.18 in CH2Cl2). HPLC
D
DAICEL CHIRALCEL IA, n-hexane/2-propanol¼80/20, flow
rate¼1.0 mL/min, ¼254 nm, retention time: 19.210 min (minor),
21.630 min (major). 1H NMR (400 MHz, CDCl3)
l
4.3.9. 3,3-Dimethyl-7-(4-nitrophenyl)-11-m-tolyl-2,4-dioxaspiro
[5.5]undecane-1,5,9-trione (5i). (C24H23NO7) a white solid; 34.5 mg,
d¼8.225 (d, 2H),
20
7.172e7.452 (m, 6H), 4.123 (dd, J1¼4.4 Hz, J2¼14.4 Hz,1H), 4.016 (dd,
J1¼4.4 Hz, J2¼14.4 Hz, 1H), 3.684 (dd, J1¼14.4 Hz, J2¼27.6 Hz, 2H),
2.673 (dt, J1¼2.0 Hz, J2¼4.4 Hz, 2H), 0.659 (s, 3H), 0.650 (s, 3H) ppm;
79% yield, 90% ee [
a
]
ꢁ1.70 (c¼2.94 in CH2Cl2). HPLC DAICEL
D
CHIRALCEL ADH, n-hexane/2-propanol¼80/20, flow rate¼1.0 mL/
min,
¼254 nm, retention time: 15.373 min (minor), 16.235 min
(major). 1H NMR (400 MHz, CDCl3)
l
13C NMR (100 MHz, CDCl3)
d
¼205.6, 167.7, 164.8, 148.0, 143.9, 135.1,
d
¼8.217 (d, 2H), 7.023e7.455 (m,
129.9, 129.7, 129.6, 124.3, 106.7, 59.9, 49.7, 49.67, 42.7, 42.4, 28.97,
28.4 ppm; HRMS (ESI-TOF) calcd for C23H20ClNO7 ([MꢁHþ])¼
456.0850, Found 456.0854.
6H), 4.127 (dd, J1¼4.0 Hz, J2¼14.4 Hz, 1H), 3.988 (dd, J1¼4.0 Hz,
J2¼14.4 Hz, 1H), 3.687 (t, J¼14.4 Hz, 2H), 2.663 (dt, J1¼4.4 Hz,
J2¼11.2 Hz, 2H), 2.326 (s, 3H), 0.677 (s, 3H), 0.532 (s, 3H) ppm; 13
C
NMR (100 MHz, CDCl3)
d
¼204.8, 167.4, 164.6, 148.1, 143.6, 141.7,
4.3.5. 7-(4-Bromophenyl)-3,3-dimethyl-11-(4-nitrophenyl)-2,4-diox-
aspiro[5.5]undecane-1,5,9-trione (5e). (C23H20BrNO7) a white solid;
133.1, 129.7, 129.5, 124.4, 113.2, 106.8, 59.6, 50.1, 49.8, 42.4, 42.2,
28.8, 28.6 ppm; HRMS (ESI-TOF) calcd for C24H23NO7 ([MꢁHþ])¼
436.1396, Found 436.1395.
20
33.7 mg, 67% yield, 85% ee [
a
]
ꢁ3.93 (c¼1.78 in CH2Cl2). HPLC
D
DAICEL CHIRALCEL IA, n-hexane/2-propanol¼80/20, flow
rate¼1.0 mL/min, ¼254 nm, retention time: 20.920 min (minor),
24.832 min (major). 1H NMR (400 MHz, CDCl3)
l
4.3.10. 7-(3-Hydroxyphenyl)-3,3-dimethyl-11-(4-nitrophenyl)-2,4-
dioxaspiro[5.5]undecane-1,5,9-trione (5j). (C23H21NO8)
solid; 28.1 mg, 64% yield, 88% ee [
HPLC DAICEL CHIRALCEL IA, n-hexane/2-propanol¼90/10, flow
rate¼1.0 mL/min, ¼254 nm, retention time: 49.972 min (major),
51.944 min (minor). 1H NMR (400 MHz, CDCl3)
d¼8.221 (d, 2H),
a
white
20
7.108e7.511 (m, 6H), 4.119 (dd, J1¼4.4 Hz, J2¼14.4 Hz, 1H), 3.999 (dd,
J1¼4.4 Hz, J2¼14.4 Hz,1H), 3.681 (dd, J1¼2.4 Hz, J2¼28.8 Hz, 2H), 2.646
(dt, J1¼2.4 Hz, J2¼4.4 Hz, 2H), 0.655 (s, 6H) ppm; 13C NMR (100 MHz,
a]
ꢁ1.27 (c¼3.24 in CH2Cl2).
D
l
CDCl3)
d
¼205.6, 167.6, 164.8, 147.9, 143.9, 135.6, 132.5, 130.2, 129.7,
d¼8.221 (d, 2H),
124.3, 123.2, 106.8, 59.8, 49.7, 49.6, 42.6, 42.4, 28.9, 28.4 ppm; HRMS
(ESI-TOF) calcd for C23H20BrNO7 ([MꢁHþ])¼500.0345, Found
500.0350.
6.696e7.451 (m, 6H), 5.016 (s, 1H), 4.135 (dd, J1¼4.4 Hz, J2¼14.4 Hz,
1H), 3.995 (dd, J1¼4.4 Hz, J2¼14.4 Hz, 1H), 3.695 (dt, J1¼7.6 Hz,
J2¼14.8 Hz, 2H), 2.678 (dt, J1¼4.4 Hz, J2¼14.0 Hz, 2H), 0.687 (s, 3H),
0.630 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3)
d¼206.5, 167.9,
4.3.6. 4-(3,3-Dimethyl-11-(4-nitrophenyl)-1,5,9-trioxo-2,4-dioxas-
piro[5.5]undecan-7-yl)benzonitrile (5f). (C24H20N2O7) a white solid;
164.96, 156.5, 147.9, 144.0, 138.3, 130.8, 129.7, 124.3, 120.5, 116.1,
115.4, 106.8, 59.9, 49.9, 49.7, 42.8, 42.5, 30.3, 29.7, 28.9, 28.3 ppm;
HRMS (ESI-TOF) calcd for C23H21NO8 ([MꢁHþ])¼438.1189, Found
438.1188.
20
36.7 mg, 82% yield, 84% ee [
a
]
ꢁ2.84 (c¼2.82 in CH2Cl2). HPLC
D
DAICEL CHIRALCEL ADH, n-hexane/2-propanol¼80/20, flow
rate¼1.0 mL/min, ¼254 nm, retention time: 41.879 min (major),
49.206 min (minor). 1H NMR (400 MHz, CDCl3)
l
d¼8.232 (d, 2H),
4.3.11. 7-(4-Hydroxyphenyl)-3,3-dimethyl-11-(4-nitrophenyl)-2,4-
dioxaspiro[5.5]undecane-1,5,9-trione (5k). (C23H21NO8)
solid; 23.7 mg, 54% yield, 95% ee [
HPLC DAICEL CHIRALCEL IA, n-hexane/2-propanol¼80/20, flow
rate¼1.0 mL/min, ¼254 nm, retention time: 16.640 min (major),
30.828 min (minor). 1H NMR (400 MHz, CDCl3)
7.369e7.690 (m, 6H), 4.137 (dd, J1¼4.4 Hz, J2¼14.4 Hz, 1H), 4.089 (dd,
J1¼4.4 Hz, J2¼14.4 Hz,1H), 3.701 (dt, J1¼5.6 Hz, J2¼14.4 Hz, 2H), 2.685
(dt, J1¼2.0 Hz, J2¼4.0 Hz, 2H), 0.635 (s, 3H), 0.627 (s, 3H) ppm; 13C
a
white
20
a]
ꢁ3.13 (c¼1.28 in CH2Cl2).
D
NMR (100 MHz, CDCl3)
d
¼204.8,167.4,164.6,148.1,143.6, 141.7,133.1,
l
129.7, 129.5, 124.4, 113.2, 106.8, 59.6, 50.1, 49.8, 42.4, 42.2, 28.8,
28.6ppm;HRMS (ESI-TOF) calcd forC24H20N2O7 ([MꢁHþ])¼447.1192,
Found 447.1200.
d¼8.215 (d, 2H),
6.797e7.446 (m, 6H), 5.140 (s, 1H), 4.102 (dd, J1¼4.4 Hz, J2¼14.4 Hz,
1H), 3.976 (dd, J1¼4.0 Hz, J2¼14.4 Hz, 1H), 3.680 (dt, J1¼9.2 Hz,
J2¼14.4 Hz, 2H), 2.649 (dt, J1¼4.8 Hz, J2¼10.0 Hz, 2H), 0.677 (s, 3H),
4.3.7. 7-(3-Methoxyphenyl)-3,3-dimethyl-11-(4-nitrophenyl)-2,4-di-
oxaspiro[5.5]undecane-1,5,9-trione (5g). (C24H23NO8) a white solid;
0.637 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3)
d¼206.4, 167.9, 165.1,
156.1, 147.9, 144.2, 129.99, 129.6, 128.8, 124.3, 116.1, 106.7, 60.3, 49.7,
49.4, 43.1, 42.5, 29.7, 28.9, 28.4 ppm; HRMS (ESI-TOF) calcd for
C23H21NO8 ([MꢁHþ])¼438.1189, Found 438.1179.
20
29.0 mg, 64% yield, 91% ee [
a
]
ꢁ2.977 (c¼2.36 in CH2Cl2). HPLC
D
DAICEL CHIRALCEL IA, n-hexane/2-propanol¼80/20, flow
rate¼1.0 mL/min, ¼254 nm, retention time: 18.478 min (major),
20.159 min (minor). 1H NMR (400 MHz, CDCl3)
l
d
¼8.215 (d, 2H),
4.3.12. 7-(Furan-2-yl)-3,3-dimethyl-11-(4-nitrophenyl)-2,4-dioxas-
6.735e7.449 (m, 6H), 4.116 (dd, J1¼4.4 Hz, J2¼14.4 Hz, 1H), 4.001
(dd, J1¼4.4 Hz, J2¼14.4 Hz, 1H), 3.781 (s, 3H), 3.717 (dd, J1¼11.2 Hz,
J2¼14.4 Hz, 2H), 2.670 (dt, J1¼4.4 Hz, J2¼15.2 Hz, 2H), 0.681 (s, 3H),
piro[5.5]undecane-1,5,9-trione (5l). (C21H19NO8)
a
white solid;
20
23.6 mg, 57% yield, 90% ee [
DAICEL CHIRALCEL IA, n-hexane/2-propanol¼80/20, flow
rate¼1.0 mL/min, ¼254 nm, retention time: 18.685 min (minor),
22.337 min (major). 1H NMR (400 MHz, CDCl3)
a]
ꢁ1.59 (c¼2.52 in CH2Cl2). HPLC
D
0.601 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3)
d¼205.8, 167.8, 160.2,
l
144.1, 138.1, 130.5, 129.7, 124.3, 120.6, 114.5, 114.2, 106.7, 59.9, 55.4,
50.0, 42.8, 42.5, 29.7, 28.9, 28.3 ppm; HRMS (ESI-TOF) calcd for
C24H23NO8 ([MꢁHþ])¼452.1345, Found 452.1346.
d
¼8.223 (d, 2H),
6.250e7.445 (m, 5H), 4.187 (dd, J1¼4.4 Hz, J2¼14.0 Hz, 1H), 4.052
(dd, J1¼4.4 Hz, J2¼14.4 Hz, 1H), 3.642 (dt, J1¼1.6 Hz, J2¼14.8 Hz, 2H),
2.649 (ddd, J1¼4.4 Hz, J2¼15.6 Hz, 2H), 0.967 (s, 3H), 0.736 (s,
4.3.8. 7-(4-Methoxyphenyl)-3,3-dimethyl-11-(4-nitrophenyl)-2,4-di-
oxaspiro[5.5]undecane-1,5,9-trione (5h). (C24H23NO8) a white solid;
3H) ppm; 13C NMR (100 MHz, CDCl3)
d¼205.2, 167.8, 164.5, 150.4,
148.0, 143.9, 142.9, 129.7, 124.3, 111.0, 109.3, 106.6, 58.3, 49.3, 43.9,