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Helvetica Chimica Acta – Vol. 97 (2014)
under H2 for 2 d. After filtration, the filtrate was concentrated under reduced pressure, and the residue
was purified by CC (SiO2) to give 2d (58.0 mg).
(1S,2S)-N,N’-Dibenzyl-N,N’-bis(2-hydroxyphenyl)cyclohexane-1,2-dicarboxamide (2d). White solid.
Yield: 58%. M.p. 254 – 2558. [a]2D0 ¼ þ17.6 (c ¼ 1.0, CHCl3). IR (CH2Cl2): 1630 (C¼O), 1270 (CꢀN),
1346, 699 (OH). 1H-NMR (CDCl3, 300 MHz): 0.77 – 1.63 (m, 4 CH2); 2.54 – 2.60 (m, 2 CH); 4.45 (d, J ¼
14.1, 2 H of 2 CH2N); 5.10 (d, J ¼ 14.1, 2 H of 2 CH2N); 6.72 – 7.28 (m, 18 arom. H); 8.57 (s, 2 OH).
13C-NMR (CDCl3, 100 MHz): 25.2; 28.1; 45.5; 53.0; 120.2; 120.8; 127.6; 128.4; 128.5; 129.1; 129.2; 129.2;
129.4; 130.1; 136.9; 152.8; 176.8. HR-MS-ESI: 535.2601 ([M þ H]þ, C34H35N2O4þ ; calc. 535.2591).
Henry Reaction: General Procedure. Ligand 2 (0.02 mmol) and CuCl (1.8 mg, 0.018 mmol) were
dissolved in anh. CH2Cl2 (1.0 ml) under N2. After stirring the soln. overnight at r.t., the solvent was
removed under reduced pressure. The residue was dissolved in EtOH (1 ml). To the resulting clear green
soln. was added MeNO2 (0.2 ml, 0.222 g, 3.64 mmol), pyridine (0.05 ml, 47.5 mg, 0.6 mmol), and aromatic
aldehyde (0.364 mmol) under N2. After stirring the mixture for 16 h at r.t., the volatile components were
removed under reduced pressure, and the residue was purified by CC (SiO2; PE/AcOEt 10 :1 (v/v) to
afford the adduct. The ee value was determined by chiral HPLC analysis (Phenomenex Lux Cellulose-1
chiral column).
1
2-Nitro-1-phenylethanol [16]. Yellow oil. Yield: 56.6 mg (93%). H-NMR (CDCl3, 300 MHz): 2.83
(br. s, OH); 4.52 (dd, J ¼ 3.0, 13.5, 1 H of CH2); 4.62 (dd, J ¼ 9.6, 13.5, 1 H of CH2); 5.45 – 5.49 (m, CH);
7.37 – 7.43 (m, 5 arom. H).
2-Nitro-1-(4-nitrophenyl)ethanol [17]. Yellow oil. Yield: 74.9 mg (97%). 1H-NMR (CDCl3,
400 MHz): 3.51 (br. s, OH); 4.59 (dd, J ¼ 4.8, 13.6, 1 H of CH2); 4.63 (dd, J ¼ 7.6, 13.6, 1 H of CH2);
5.62 (dd, J ¼ 4.8, 7.6, CH); 7.63 (d, J ¼ 8.8, 2 arom. H); 8.22 (d, J ¼ 8.8, 2 arom. H).
1-(4-Chlorophenyl)-2-nitroethanol [17]. Yellow oil. Yield: 69.7 mg (95%). 1H-NMR (CDCl3,
400 MHz): 2.89 (br. s, OH); 4.49 (dd, J ¼ 3.2, 13.6, 1 H of CH2); 4.58 (dd, J ¼ 9.6, 13.6, 1 H of CH2);
5.44 – 5.48 (m, CH); 7.35 (d, J ¼ 8.8, 2 arom. H); 7.39 (d, J ¼ 8.8, 2 arom. H).
1-(4-Methylphenyl)-2-nitroethanol [17]. Yellow oil: 31.0 mg (47%). 1H-NMR (CDCl3, 400 MHz):
2.36 (s, Me); 2.72 (br. s, OH); 4.49 (dd, J ¼ 3.2, 13.2, 1 H of CH2); 4.60 (dd, J ¼ 9.6, 13.2, 1 H of CH2);
5.41 – 5.45 (m, CH); 7.21 (d, J ¼ 8.0, 2 arom. H); 7.29 (d, J ¼ 8.0, 2 arom. H).
1-(4-Methoxyphenyl)-2-nitroethanol [17]. Yellow oil: 13.6 mg (19%). 1H-NMR (CDCl3, 400 MHz):
3.13 (br. s, OH); 3.78 (s, MeO); 4.43 (dd, J ¼ 3.2, 13.2, 1 H of CH2); 4.56 (dd, J ¼ 9.6, 13.2, 1 H of CH2);
5.43 (dd, J ¼ 3.2, 9.6, CH); 6.89 (d, J ¼ 8.8, 2 arom. H); 7.27 (d, J ¼ 8.8, 2 arom. H).
The project was supported by the National Basic Research Program of China (No 2013CB328905),
the National Natural Science Foundation of China (Nos. 21372025, 21172017, and 20092013), and the
Doctoral Fund of Ministry of Education of China (20110010110011).
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