Z. Ma et al. / Tetrahedron: Asymmetry 23 (2012) 443–448
447
(d, 2H, J = 8.4 Hz), 7.46 (d, 2H, J = 8.4 Hz). 13C NMR (CDCl3,
100 MHz): 29.7, 30.5, 42.2, 70.4, 77.8, 122.7, 129.7, 132.5, 135.1,
200.6, 201.4. HPLC analysis (Chiralpak AD-H column, i-propanol/
hexane = 85/15, flow rate = 0.6 mL/min, wavelength = 210 nm):
Rt = 21.4 min (major), 74.6 min (minor).
70.7, 78.2, 125.0, 126.7, 126.8, 127.5, 127.7, 128.0, 129.4, 133.0,
133.3, 201.0, 201.8. HPLC analysis (Chiralpak AD-H column, i-pro-
panol/hexane = 15/1,
flow
rate = 0.7 mL/min,
wave-
length = 210 nm): Rt = 40.6 min (major), 54.3 min (minor).
4.3.11. (R)-3-[1-(Furan-2-yl)-2-nitroethyl]pentane-2,4-dione
9k4d
4.3.5. (S)-3-(2-Nitro-1-(2-nitrophenyl)ethyl)pentane-2,4-dione
9e6c
1H NMR (CDCl3, 400 MHz): d = 2.09 (s, 3H), 2.28 (s, 3H), 4.33–
4.41 (m, 2H), 4.67 (d, 2H, J = 5.6 Hz), 6.18 (d, 1H, J = 3.6 Hz), 6.31
(dd, 1H, J = 3.2, 2.0 Hz), 7.36 (m, 1H). 13C NMR (CDCl3, 100 MHz):
29.3, 30.7, 36.6, 67.9, 75.8, 108.9, 110.8, 142.9, 149.4, 200.8,
201.5. HPLC analysis (Chiralpak AD-H column, i-propanol/hexane =
40/1, flow rate = 0.75 mL/min, wavelength = 210 nm): Rt =
35.2 min (major), 44.8 min (minor).
1H NMR (CDCl3, 400 MHz): d = 2.14 (s, 3H), 2.32 (s, 3H), 4.68 (d,
1H, J = 8.8 Hz), 4.74 (dt, 1H, J = 8.0, 6.8 Hz), 4.84 (dd, 1H, J = 13.6,
3.6 Hz), 4.97 (dd, 1H, J = 13.2, 7.2 Hz), 7.36 (d, 1H, J = 7.6 Hz), 7.49
(t, 1H, J = 8.0 Hz), 7.59 (t, 1H, J = 7.6 Hz), 7.93 (d, 1H, J = 8.0 Hz). 13
C
NMR (CDCl3, 100 MHz): 29.4, 31.3, 37.1, 69.1, 76.6, 125.6, 129.2,
129.4, 131.2, 133.5, 149.8, 200.6, 201.6. HPLC analysis (Chiralcel
OD-H column, i-propanol/hexane = 90/10, flow rate = 0.7 mL/min,
wavelength = 210 nm): Rt = 71.6 min (major), 92.2 min (minor).
4.3.12. (R)-3-(1-(5-Chlorothiophen-2-yl)-2-nitroethyl)pentane-
2,4-dione 9l
4.3.6. (S)-3-[1-(4-Methylphenyl)-2-nitroethyl]pentane-2,4-
dione 9f4d
1H NMR (CDCl3, 400 MHz): d = 1.16 (s, 6H), 1.47 (s, 3H), 2.06 (s,
1H), 2.31 (s, 2H), 3.92 (d, 0.3H, J = 9.6 Hz), 4.01 (d, 0.7H,
J = 10.4 Hz), 4.66–4.76 (m, 1.4H), 4.79–4.89 (m, 0.7H), 7.20–7.22
(m, 2H), 7.27–7.33 (m, 3H). 13C NMR (CDCl3, 100 MHz): 27.4,
27.8, 29.7, 30.1, 42.3, 42.5, 62.7, 63.0, 82.9, 83.5, 128.0, 128.2,
128.3, 128.8, 129.1, 136.6, 165.8, 166.6, 200.6, 201.4. HPLC analysis
(Chiralpak AD-H column, i-propanol/hexane = 95/5, flow rate =
0.7 mL/min, wavelength = 215 nm): major diastereomer: Rt =
14.4 min (major), 20.3 min (minor); minor diastereomer:
22.2 min (minor), 41.6 min (major)
1H NMR (CDCl3, 400 MHz): d = 1.97 (s, 3H), 2.29 (s, 3H), 3.78 (s,
3H), 4.19–4.24 (m, 1H), 4.37 (d, 1H, J = 10.8 Hz), 4.61–4.63 (m, 2H),
6.72–6.83 (m, 3H), 7.22–7.27 (m, 1H). 13C NMR (CDCl3, 100 MHz):
29.6, 30.5, 42.8, 55.2, 70.6, 78.1, 113.6, 114.1, 119.9, 130.4, 137.6,
160.1, 201.0, 201.8. HPLC analysis (Chiralpak AD-H column,
i-propanol/hexane = 85/15, flow rate = 0.65 mL/min, wavelength =
210 nm): Rt = 16.9 min (major), 22.4 min (minor).
4.3.7. (S)-3-[1-(3-Methoxyphenyl)-2-nitroethyl]pentane-2,4-
dione 9g4d
4.3.13. (R)-3-[(E)-1-Nitro-4-phenylbut-3-en-2-yl)pentane-2,4-
dione 9m4d
1H NMR (CDCl3, 400 MHz): d = 1.97 (s, 3H), 2.29 (s, 3H), 3.78 (s,
3H), 4.19–4.24 (m, 1H), 4.37 (d, 1H, J = 10.8 Hz), 4.60–4.67 (m, 2H),
7.16 (t, 1H, J = 2.0 Hz), 6.76 (d, 1H, J = 7.6 Hz), 6.81 (dd, 2H, J = 2.0,
8.0 Hz), 7.24 (t, 1H, J = 8.0 Hz). 13C NMR (CDCl3, 100 MHz): 29.7,
30.5, 42.8, 55.2, 70.6, 78.1, 113.6, 114.2, 119.9, 130.4, 137.6,
160.1, 201.0, 201.8. HPLC analysis (Chiralpak AD-H column,
i-propanol/hexane = 85/15, flow rate = 0.5 mL/min, wavelength =
210 nm): Rt = 21.3 min (major), 28.0 min (minor).
1H NMR (CDCl3, 400 MHz): d = 2.21 (s, 3H), 2.28 (s, 3H), 3.70–
3.77 (m, 1H), 4.06 (d, 1H, J = 9.2 Hz), 4.52–4.59 (m, 2H), 6.02 (dd,
1H, J = 16.0, 9.6 Hz), 6.55 (d, 1H, J = 16.0 Hz), 7.25–7.31 (m, 5H).
13C NMR (CDCl3, 100 MHz): 30.0, 30.6, 40.9, 69.1, 77.4, 123.1,
126.6, 128.5, 128.7, 135.6, 201.6, 201.9. HPLC analysis (Chiralpak
AD-H column, i-propanol/hexane = 90/10, flow rate = 0.7 mL/min,
wavelength = 210 nm): Rt = 20.3 min (major), 26.0 min (minor).
4.3.14. (3S)-tert-Butyl 2-acetyl-4-nitro-3-phenylbutanoate 1111
1H NMR (CDCl3, 400 MHz): d = 1.16 (s, 6H), 1.47 (s, 3H), 2.06 (s,
1H), 2.31 (s, 2H), 3.92 (d, 0.3H, J = 9.6 Hz), 4.01 (d, 0.7H,
J = 10.4 Hz), 4.11–4.22 (m, 1H), 4.66–4.76 (m, 1.4H), 4.79–4.89
(m, 0.7H), 7.20–7.22 (m, 2H), 7.27–7.33 (m, 3H). 13C NMR (CDCl3,
100 MHz): 27.4, 27.8, 29.7, 30.1, 42.3, 42.5, 62.7, 63.0, 82.9, 83.5,
128.0, 128.2, 128.3, 128.8, 129.1, 136.6, 165.8, 166.6, 200.6,
201.4. HPLC analysis (Chiralpak AD-H column, i-propanol/
hexane = 95/5, flow rate = 0.7 mL/min, wavelength = 215 nm): the
major diastereomer: Rt = 14.4 min (major), 20.3 min (minor); the
minor diastereomer: 22.2 min (minor), 41.6 min (major).
4.3.8. (S)-3-[1-(4-Methoxyphenyl)-2-nitroethyl]pentane-2,4-
dione 9h4d
1H NMR (CDCl3, 400 MHz): d = 1.94 (s, 3H), 2.29 (s, 3H), 3.77 (s,
3H), 4.18–4.23 (m, 1H), 4.33 (d, 1H, J = 10.8 Hz), 4.59 (d, 2H,
J = 6.4 Hz), 6.84 (d, 2H, J = 8.4 Hz), 7.10 (d, 2H, J = 8.8 Hz). 13C
NMR (CDCl3, 100 MHz): 29.5, 30.4, 42.1, 55.2, 70.9, 78.5, 114.7,
127.6, 129.1, 159.5, 201.2, 201.9. HPLC analysis (Chiralpak AD-H
column, i-propanol/hexane = 85/15, flow rate = 0.65 mL/min,
wavelength = 210 nm): Rt = 21.2 min (major), 33.4 min (minor).
4.3.9. (S)-3-[1-(Naphthalen-1-yl)-2-nitroethyl]pentane-2,4-
dione 9i4d
1H NMR (CDCl3, 400 MHz): d = 1.86 (s, 3H), 2.31 (s, 3H), 4.69–
4.75 (m, 2H), 4.81 (dd, 1H, J = 12.0, 8.4 Hz), 5.20 (m, 1H), 7.27 (d,
1H, J = 7.2 Hz), 7.40 (t, 1H, J = 7.6 Hz), 7.54 (t, 1H, J = 7.2 Hz), 7.63
(dt, 1H, J = 7.6, 1.2 Hz), 7.80 (d, 1H, J = 8.0 Hz), 8.17 (d, 1H,
J = 8.4 Hz). 13C NMR (CDCl3, 100 MHz): 28.7, 31.1, 36.3, 70.4,
77.8, 121.9, 124.8, 125.3, 126.3, 127.4, 129.2, 129.5, 130.8, 131.9,
134.3, 200.8, 202.4. HPLC analysis (AE.LICHROM-AM2–5 column,
i-propanol/hexane = 40/1, flow rate = 0.8 mL/min, wavelength =
210 nm): Rt = 109.2 min (major), 149.8 min (minor).
Acknowledgments
We are grateful for the financial support of the National Natural
Science Foundation of China (NSFC 20772113) and the Doctoral
Foundation of Henan Institute of Engineering (D09002).
References
1. For reviews, see: (a) Burke, M. D.; Schreiber, S. L. Angew. Chem., Int. Ed. 2004, 43,
46–58; (b) Zanoni, G.; Castronovo, F.; Franzini, M.; Vidari, G.; Giannini, E. Chem.
Soc. Rev. 2003, 32, 115–129.
2. For some selected examples: (a) Jiang, X.-X.; Zhang, Y.-F.; Chan, A. S. C.; Wang,
R. Org. Lett. 2009, 11, 153–156; (b) Chen, J.-R.; Cao, Y.-J.; Zou, Y.-Q.; Tan, F.; Fu,
L.; Zhu, X.-Y.; Xiao, W.-J. Org. Biomol. Chem. 2010, 8, 1275–1279; (c) Pu, X.-W.;
Peng, F.-Z.; Zhang, H.-B.; Shao, Z.-H. Tetrahedron 2010, 66, 3655–3661; (d)
Chen, J.-R.; Zou, Y.-Q.; Fu, L.; Ren, F.; Tan, F.; Xiao, W.-J. Tetrahedron 2010, 66,
5367–5372.
4.3.10. (S)-3-[1-(Naphthalen-2-yl)-2-nitroethyl]pentane-2,4-
dione 9j
1H NMR (CDCl3, 400 MHz): d = 1.94 (s, 3H), 2.31 (s, 3H), 4.39–
4.45 (m, 1H), 4.50 (d, 1H, J = 10.8 Hz), 4.67–4.77 (m, 2H), 7.30
(dd, 1H, J = 8.8, 1.6 Hz), 7.47–7.51 (m, 2H), 7.65 (d, 1H, J = 1.2 Hz),
7.77–7.84 (m, 3H). 13C NMR (CDCl3, 100 MHz): 29.6, 30.5, 42.9,