10.1002/ejoc.201900719
European Journal of Organic Chemistry
FULL PAPER
– 7.27 (m, 3H), 7.20 – 7.16 (m, 2H), 4.66 (dd, J = 12.5, 4.4 Hz, 1H), 4.56
(dd, J = 12.5, 9.9 Hz, 1H), 3.89 (td, J = 10.3, 4.4 Hz, 1H), 2.76 (ddd, J =
10.7, 4.1, 2.4 Hz, 1H), 1.73 – 1.67 (m, 1H), 1.09 (d, J = 7.2 Hz, 3H), 0.87
(d, J = 7.0 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ 204.4, 137.1,
129.2, 128.1, 128.0, 79.0, 58.8, 42.0, 28.0, 21.7, 17.0 ppm; HRMS (ESI-
TOF) m/z: [M−H]− calcd for C13H16NO3 234.1130, found 234.1117; HPLC
(Chiralpak IC column, Hexane:2–Propanol = 99:1, flow rate: 1 mL/min, λ
= 254 nm), tR major= 14.77, tR minor= 17.40, 95% ee and >99:1 dr.
196.0625; HPLC (Chiralpak IC column, Hexane:2–Propanol = 90:10, flow
rate: 1 mL/min, λ = 254 nm), tR major= 15.21, tR minor = 21.05, 95% ee
and 79:21 dr.
Acknowledgements
(2S,3R)-2-methyl-4-nitro-3-(p-tolyl)butanal
(4k).
Column
We thank the Science and Engineering Research Board,
Department of Science and Technology India for funding this
project through EMR/2017/000414. We thank Prof. D. H. Dethe
for helping us with HPLC analysis.
chromatography (85:15 petroleum ether/EtOAc); Pale yellow oil (0.10 g,
93% Yield); 1H NMR (400 MHz, CDCl3) δ 9.69 (d, J = 1.8 Hz, 1H), 7.12 –
7.10 (m, 2H), 7.03 (d, J = 8.1 Hz, 2H), 4.75 (dd, J = 6.7, 3.1 Hz, 1H), 4.67
– 4.61 (m, 1H), 3.76 (dd, J = 9.0, 3.3 Hz, 1H), 2.77 – 2.71 (m, 1H), 2.31
(s, 3H), 0.98 (d, J = 7.2 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ
202.5, 137.9, 133.4, 129.8, 127.9, 78.3, 48.5, 43.7, 21.1, 12.1 ppm;
HRMS (ESI-TOF) m/z: [M−H]− calcd for C12H14NO3 220.0974, found
220.0987; HPLC (Chiralpak IC column, Hexane:2–Propanol = 90:10, flow
rate: 1 mL/min, λ = 254 nm), tR major = 20.70, tR minor = 25.47, 95% ee
and 73:27 dr.
Keywords: Michael addition • organocatalysis • aldehydes •
nitroalkenes • enantioselectivity
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(2S,3R)-3-(4-fluorophenyl)-2-methyl-4-nitrobutanal
(4l).
Column
chromatography (80:20 petroleum ether/EtOAc); Pale yellow oil (0.10 g,
88% Yield); 1H NMR (400 MHz, CDCl3) δ 9.68 (d, J = 1.3 Hz, 1H), 7.18–
7.12 (2H), 7.04 – 7.00 (m, 2H), 4.78 – 4.74 (m, 1H), 4.65 – 4.60 (m, 1H),
3.79 (td, J = 9.3, 5.3 Hz, 1H), 2.79 – 2.71 (m, 1H), 0.98 (d, J = 7.3 Hz, 3H
ppm; 13C NMR (100 MHz, CDCl3) δ 202.1, 162.4 (d, J = 247.3 Hz), 132.4
(d, J = 2.9 Hz), 129.7 (d, J = 8.2 Hz), 116.1 (d, J = 21.7 Hz), 78.2, 48.4,
43.3, 12.2 ppm; HRMS (ESI-TOF) m/z: [M−H]− calcd for C11H11FNO3
224.0723, found 224.0723; HPLC (Chiralpak IC column, Hexane:2–
Propanol = 90:10, flow rate: 1 mL/min, λ = 254 nm), tR major= 21.23, tR
minor = 25.00, 97% ee and 78:22 dr.
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(2S,3R)-3-(4-methoxyphenyl)-2-methyl-4-nitrobutanal (4m). Column
chromatography (80:20 petroleum ether/EtOAc); Pale yellow oil (0.10 g,
92% Yield); 1H NMR (400 MHz, CDCl3) δ 9.69 (d, J = 1.7 Hz, 1H), 7.06
(d, J = 8.6 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H), 4.75 (dd, J = 7.5, 2.1 Hz, 1H),
4.65 – 4.59 (m, 1H), 3.77 (s, 3H), 3.76 – 3.72 (m, 1H), 2.76-2.68(m, 1H),
0.99 (d, J = 7.3 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ 202.5, 159.3,
129.1, 128.3, 114.5, 78.4, 55.3, 48.6, 43.4, 12.1 ppm; HRMS (ESI-TOF)
m/z: [M−H]− calcd for C12H14NO4 236.0923, found 236.0920; HPLC
(Chiralpak IC column, Hexane:2–Propanol = 90:10, flow rate: 1 mL/min, λ
= 254 nm), tR major= 30.43, tR minor = 35.08, 95% ee and 82:18 dr.
(2S,3R)-3-(3-chlorophenyl)-2-methyl-4-nitrobutanal (4n).
Column
chromatography (80:20 petroleum ether/EtOAc); Pale yellow oil (0.10 g,
85% Yield); 1H NMR (400 MHz, CDCl3) δ 9.69 (d, J = 1.4 Hz, 1H), 7.28–
7.25 (m, 2H), 7.16 (s, 1H), 7.07 – 7.04 (m, 1H), 4.77 (d, J = 5.0 Hz, 1H),
4.67 – 4.61 (m, 1H), 3.77 (dd, J = 9.2, 4.0 Hz, 1H), 2.82 – 2.74 (m, 1H),
1.01 (d, J = 7.4 Hz, 3H) ppm; 13C NMR (100 MHz, CDCl3) δ 201.7, 138.8,
135.0, 130.4, 128.5, 128.3, 126.4, 77.8, 48.2, 43.7, 12.3 ppm; HRMS
(ESI-TOF) m/z: [M−H]− calcd for C11H11ClNO3 240.0427, found 240.0426;
HPLC (Chiralpak IC column, Hexane:2–Propanol = 90:10, flow rate: 1
mL/min, λ = 254 nm), tR major= 20.07, tR minor = 23.61, 97% ee and
76:24 dr.
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2006, 12, 4321–4332.
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(2S,3S)-3-(furan-2-yl)-2-methyl-4-nitrobutanal
(4o).
Column
chromatography (85:15 petroleum ether/EtOAc); Pale yellow oil (0.09 g,
93% Yield); 1H NMR (400 MHz, CDCl3) δ 9.70 (d, J = 0.8 Hz, 1H), 7.35
(dd, J = 3.2, 1.4 Hz, 1H), 6.29 (dd, J = 3.3, 1.8 Hz, 1H), 6.18 (dd, J = 8.5,
3.2 Hz, 1H), 4.71 (dd, J = 8.2, 6.9 Hz, 2H), 4.10 – 4.04 (m, 1H), 2.79 (dd,
J = 7.3, 6.7 Hz, 1H), 1.06 (d, J = 7.3 Hz, 3H) ppm; 13C NMR (100 MHz,
CDCl3) δ 201.6, 149.9, 142.7, 110.5, 108.8, 75.8, 47.1, 37.7, 11.0 ppm;
HRMS (ESI-TOF) m/z: [M−H]− calcd for C9H10NO4 196.0610, found
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