S. Ma et al. / Tetrahedron 69 (2013) 2613e2618
2617
column [hexane/i-PrOH (80:20)]; flow rate 1.0 mL minꢀ1
major¼30.1 min, minor¼48.9 min (79% ee).
;
i-PrOH (80:20)]; flow rate 1.0 mL minꢀ1
minor¼34.6 min (60% ee).
;
major¼28.9 min,
4.2.7. 2-(1-(2-Methoxyphenyl)-2-nitroethyl)-5-nitroisoindoline-1,3-
4.2.12. 2-(1-(Naphthalen-1-yl)-2-nitroethyl)-5-nitroisoindoline-1,3-
25
dione (4bg). White solid, mp: 160e161 ꢁC, 57% yield, [
a]
25 ꢀ163.75
dione (4bl). Yellow solid, mp: 89e91 ꢁC, 62% yield, [
a]
þ14.66
D
D
(c 0.2, CH2Cl2). 1H NMR (400 MHz, CDCl3)
d
8.66 (s, 1H), 8.62
(c 0.2, CH2Cl2). 1H NMR (400 MHz, CDCl3)
d
8.65 (s, 1H), 8.60
(d, J¼8.1 Hz,1H), 8.06 (d, J¼8.1 Hz,1H), 7.33 (dt, J¼24.0,14.6 Hz, 2H),
7.03e6.86 (m, 2H), 6.53 (dd, J¼11.0, 3.6 Hz, 1H), 5.72 (dd, J¼13.7,
11.3 Hz, 1H), 4.96 (dd, J¼14.0, 3.8 Hz, 1H), 3.90 (s, 3H). 13C NMR
(d, J¼8.1 Hz, 1H), 8.39 (d, J¼8.6 Hz, 1H), 8.05 (d, J¼8.1 Hz, 1H), 7.90
(t, J¼10.2 Hz, 2H), 7.80 (t, J¼10.3 Hz, 1H), 7.67 (dd, J¼15.7, 7.6 Hz,
1H), 7.61e7.48 (m, 2H), 7.02 (dd, J¼10.9, 3.8 Hz, 1H), 6.01 (dd,
J¼13.5, 11.1 Hz, 1H), 5.12 (dd, J¼13.6, 3.9 Hz, 1H). 13C NMR (101 MHz,
(101 MHz, CDCl3)
d 165.83, 165.55, 156.30, 151.93, 135.90, 132.95,
130.58, 129.56, 127.87, 124.92, 121.85, 120.86, 119.07, 111.03, 73.10,
55.74, 47.93. HRMS calcd for C17H13N3O7Na, [MþNa]þ 394.0651,
found 394.0647. The ee was determined by HPLC using a Chiralpak
CDCl3) d 165.80, 165.54, 151.92, 135.70, 133.99, 132.79, 130.42,
129.65, 129.33, 129.14, 127.77, 126.47, 126.39, 125.10, 125.01, 122.20,
119.15, 74.21, 48.61. HRMS calcd for C22H13N3O6Na, [MþNa]þ
414.0702, found 414.0696. The ee was determined by HPLC using
a Chiralpak AS-H column [hexane/i-PrOH (60:40)]; flow rate
0.9 mL minꢀ1; major¼47.6 min, minor¼54.8 min (85% ee).
AD-H column [hexane/i-PrOH (80:20)]; flow rate 1.0 mL minꢀ1
minor¼29.0 min, major¼35.2 min (71% ee).
;
4.2.8. 2-(1-(2-Chlorophenyl)-2-nitroethyl)-5-nitroisoindoline-1,3-
25
dione (4bh). White solid, mp: 46e48 ꢁC, 61% yield, [
a]
þ50.30
4.2.13. 5-Nitro-2-(2-nitro-1-(thiophen-2-yl)ethyl)isoindoline-1,3-
D
25
(c 0.2, CH2Cl2). 1H NMR (400 MHz, CDCl3)
d
8.68 (s, 1H), 8.64
dione (4bm). Yellow solid, mp: 50e51 ꢁC, 66% yield, [
a]
þ6.00
D
(d, J¼8.2 Hz, 1H), 8.07 (t, J¼10.7 Hz, 1H), 7.61e7.54 (m, 1H), 7.46
(d, J¼7.1 Hz, 1H), 7.39e7.28 (m, 2H), 6.61 (dd, J¼11.0, 4.0 Hz, 1H),
5.75 (dd, J¼14.0, 11.1 Hz, 1H), 4.96 (dd, J¼14.1, 4.1 Hz, 1H). 13C NMR
(c 0.2, CH2Cl2). 1H NMR (400 MHz, CDCl3)
d
8.67 (d, J¼1.6 Hz, 1H),
8.62 (dd, J¼8.1, 1.9 Hz, 1H), 8.06 (t, J¼8.8 Hz, 1H), 7.33 (t, J¼6.8 Hz,
1H), 7.27 (d, J¼3.4 Hz, 1H), 7.04e6.99 (m, 1H), 6.44 (dd, J¼10.6,
4.8 Hz, 1H), 5.78 (dd, J¼13.9, 10.6 Hz, 1H), 5.12e4.97 (m, 1H). 13C
(101 MHz, CDCl3)
d 165.63, 165.42, 152.03, 135.66, 133.30, 132.76,
131.48, 130.76, 130.51, 129.76, 128.97, 127.62, 125.14, 119.26, 72.83,
50.03. HRMS calcd for C16H10Cl2N3O6, [MþCl]ꢀ 409.9947, found
409.9952. The ee was determined by HPLC using a Chiralpak AD-H
NMR (101 MHz, CDCl3) d 165.09, 164.84, 151.99, 135.73, 135.27,
132.81, 129.74, 128.30, 127.31, 125.13, 119.25, 74.28, 47.74. HRMS
calcd for C15H13N3O7SNa, [MþNaþCH3OH]þ 402.0372, found
402.0361. The ee was determined by HPLC using a Chiralpak AD-H
column [hexane/i-PrOH (80:20)]; flow rate 1.0 mL minꢀ1
minor¼30.5 min, major¼32.3 min (64% ee).
;
column [hexane/i-PrOH (80:20)]; flow rate 1.0 mL minꢀ1
major¼37.5 min, minor¼43.8 min (87% ee).
;
4.2.9. 5-Nitro-2-(2-nitro-1-(2-(trifluoromethyl)
phenyl)ethyl)iso-
indoline-1,3-dione (4bi). White solid, mp: 36e38 ꢁC, 64% yield,
4.2.14. 2-(1-(Furan-2-yl)-2-nitroethyl)-5-nitroisoindoline-1,3-dione
25
25
[
a]
þ57.08 (c 0.2, CH2Cl2). 1H NMR (400 MHz, CDCl3)
d
8.69
(4bn). Yellow solid, mp: 28e29 ꢁC, 63% yield, [
a
]
ꢀ44.44 (c 0.2,
D
D
(s, 1H), 8.65 (d, J¼8.1 Hz, 1H), 8.09 (d, J¼8.1 Hz, 1H), 7.89
(d, J¼7.9 Hz, 1H), 7.77 (d, J¼7.8 Hz, 1H), 7.62 (t, J¼7.6 Hz, 1H), 7.53
(t, J¼7.6 Hz, 1H), 6.56 (dd, J¼11.3, 3.5 Hz, 1H), 5.92 (dd, J¼14.6,
11.5 Hz, 1H), 4.78 (dd, J¼14.7, 3.6 Hz, 1H). 13C NMR (101 MHz,
CH2Cl2). 1H NMR (400 MHz, CDCl3)
d
8.68 (t, J¼4.2 Hz, 1H), 8.63 (dt,
J¼9.2, 4.6 Hz,1H), 8.07 (t, J¼8.9 Hz,1H), 7.38 (dd, J¼14.2, 5.6 Hz,1H),
6.45 (t, J¼6.3 Hz, 1H), 6.43e6.35 (m, 1H), 6.28 (dt, J¼16.0, 7.9 Hz,
1H), 5.64 (dd, J¼14.1, 10.3 Hz, 1H), 5.16e5.02 (m, 1H). 13C NMR
CDCl3)
d
166.01, 165.86, 152.10, 135.56, 133.03, 132.71, 129.89,
(101 MHz, CDCl3) d 164.97, 164.71, 152.00, 143.42, 135.74, 132.84,
129.81, 129.68, 127.02, 126.97, 125.16, 119.26, 73.13, 50.04, 25.37.
HRMS calcd for C17H10ClF3N3O6, [MþCl]ꢀ 444.0210, found
444.0201. The ee was determined by HPLC using a Chiralpak AD-H
130.93, 129.72, 125.13, 119.26, 110.94, 109.62, 72.53, 46.11. HRMS
calcd for C15H13N3O8Na, [MþNaþCH3OH]þ 386.0600, found
386.0599. The ee was determined by HPLC using a Chiralpak AD-H
column [hexane/i-PrOH (80:20)]; flow rate 1.0 mL minꢀ1
major¼17.4 min, minor¼19.3 min (62% ee).
;
column [hexane/i-PrOH (80:20)]; flow rate 1.0 mL minꢀ1
major¼34.0 min, minor¼44.5 min (87% ee).
;
4.2.10. 2-(1-(3-Chlorophenyl)-2-nitroethyl)-5-nitroisoindoline-1,3-
4.2.15. 2-(1-Cyclohexyl-2-nitroethyl)-5-nitroisoindoline-1,3-dione
25
dione (4bj). White solid, mp: 49e51 ꢁC, 69% yield, [
a
]
þ8.52
(4bo). Colorless oil, 75% yield, [
a
]
25 ꢀ19.23 (c 0.2, CH2Cl2). 1H NMR
D
D
(c 0.2, CH2Cl2). 1H NMR (400 MHz, CDCl3)
d
8.70 (s, 1H), 8.64
(400 MHz, CDCl3)
d
8.68 (d, J¼1.5 Hz, 1H), 8.64 (dd, J¼8.1, 1.8 Hz,
(t, J¼10.7 Hz,1H), 8.08 (t, J¼12.3 Hz,1H), 7.54 (d, J¼14.7 Hz,1H), 7.45
(d, J¼6.1 Hz, 1H), 7.42e7.33 (m, 2H), 6.15 (dd, J¼10.5, 4.6 Hz, 1H),
5.95e5.74 (m,1H), 5.04 (dt, J¼25.0, 12.5 Hz, 1H). 13C NMR (101 MHz,
1H), 8.07 (d, J¼8.1 Hz, 1H), 5.28 (dd, J¼12.8, 11.0 Hz, 1H), 4.88e4.69
(m, 2H), 2.10 (dt, J¼8.8, 8.3 Hz, 1H), 1.84 (d, J¼9.5 Hz, 2H), 1.70
(t, J¼10.6 Hz, 2H), 1.54 (d, J¼12.5 Hz, 1H), 1.35e1.13 (m, 4H),
CDCl3)
d
165.49, 165.24, 152.03, 136.00, 135.67, 135.37, 132.77,
1.09e0.94 (m, 1H). 13C NMR (101 MHz, CDCl3)
d 165.88, 165.60,
130.76, 129.90, 129.78, 128.25, 126.16, 125.15, 119.28, 73.45, 52.21.
HRMS calcd for C16H10Cl2N3O6, [MþCl]ꢀ 409.9947, found 409.9953.
The ee was determined by HPLC using a Chiralpak AD-H column
[hexane/i-PrOH (80:20)]; flow rate 1.0 mL minꢀ1; major¼28.6 min,
minor¼30.1 min (68% ee).
151.96, 135.63, 132.72, 129.61, 124.93, 119.09, 73.68, 55.02, 37.59,
30.35, 29.56, 25.66, 25.42, 25.37. HRMS calcd for C16H17N3O6Na,
[MþNa]þ 370.1015, found 370.1008. The ee was determined by
HPLC using a Chiralpak AD-H column [hexane/i-PrOH (80:20)];
flow rate 1.0 mL minꢀ1
;
major¼19.3 min, minor¼24.9 min
(65% ee).
4.2.11. 2-(1-(2,4-Dichlorophenyl)-2-nitroethyl)-5-nitroisoindoline-
1,3-dione (4bk). White solid, mp: 76e78 ꢁC, 51% yield, [
a
]
25 þ3.22
D
(c 0.2, CH2Cl2). 1H NMR (400 MHz, CDCl3)
d
8.69 (s, 1H), 8.65
Acknowledgements
(d, J¼8.2 Hz, 1H), 8.09 (d, J¼8.1 Hz, 1H), 7.55 (d, J¼8.5 Hz, 1H), 7.48
(s, 1H), 7.31 (d, J¼8.5 Hz, 1H), 6.56 (dd, J¼10.7, 4.2 Hz, 1H), 5.70 (dd,
J¼13.7, 11.1 Hz, 1H), 4.94 (dd, J¼14.0, 4.2 Hz,1H). 13C NMR (101 MHz,
This work was financially supported by the Ph.D. Programs
Foundation of Ministry and Education of China (no.
20090031110019) and National Basic Research Program of China
(973 Program) (no. 2010CB833300). We also thank the Nankai
University State Key Laboratory of Elemento-Organic Chemistry for
support.
CDCl3)
d 165.50, 165.29, 152.10, 136.30, 135.55, 134.22, 132.68,
130.35, 130.04, 129.85, 127.96, 125.22, 119.33, 72.73, 49.39. HRMS
calcd for C16H9Cl3N3O6, [MþCl]ꢀ 443.9557, found 443.9557. The ee
was determined by HPLC using a Chiralpak AD-H column [hexane/