2,4-Dinitrobenzoic acid → HCID 86588405, compound

HRID 1837855Notes

Reaction equation

HRID 1837855 reaction equation
[CH2:1]([O:8][CH2:9][CH:10]=[CH:11][CH:12]=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(O)(=O)C1C=CC=CC=1.[CH3:23][C:24]1[CH:32]=[CH:31][CH:30]=[C:29]2[C:25]=1[CH:26]=[CH:27][NH:28]2.[N+](C1C=C([N+]([O-])=O)C=CC=1C(O)=O)([O-])=O.C([C@@H]1N[C@H](C(C)(C)C)N(C)C1=O)C1C=CC=CC=1>C(Cl)Cl.C(O)(C)C>[CH2:1]([O:8][CH2:9][C@@H:10]([C:26]1[C:25]2[C:29](=[CH:30][CH:31]=[CH:32][C:24]=2[CH3:23])[NH:28][CH:27]=1)[CH2:11][CH:12]=[O:13])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 4

HCID 118802,4-Dinitrobenzoic acidHCID 852824-MethylindoleHCID 103098345-Benzyl-2-tert-butyl-3-methyl-4-imidazolidinone, (2S,5S)-HCID 86588406HCID 86588406, compound

Product 1

HCID 86588405HCID 86588405, compoundYield 97.6%

Reagents, catalysts & solvents 2

HCID 3776IsopropanolSolventHCID 6344DichloromethaneSolvent

Procedure

Prepared according to the general procedure from benzoic acid 4-benzyloxy-but-enal (143 mg, 0.750 mmol), 4-methyl-1H-indole (80.5 mg, 0.500 mmol), 2,4-dinitrobenzoic acid (21.2 mg, 0.100 mmol) and (2S,5S)-5-benzyl-2-tert-butyl-3-methyl-imidazolidin-4-one (24.6 mg, 0.100 mmol) in CH2Cl2 (0.90 mL) and isopropanol (0.10 mL) at −60° C. for 2.5 h to provide, after silica gel chromatography (15:85 EtOAc/hexanes), the title compound as a colorless oil (150 mg, 94% yield, 94% ee) after silica gel chromatography in 15% EtOAc/hexanes. IR (film) 3406, 2947, 2923, 2843, 2738, 1717, 1620, 1604, 1584, 1451, 1411, 1383, 1344, 1315, 1271, 1178, 1114, 1066, 1226, 969 cm−1; 1H NMR (300 MHz, CDCl3) δ 9.82 (dd, J=2.1, 2.1 Hz, 1H, CHO), 8.14 (s, 1H, NH), 8.02 (dt, J=1.5, 7.2 Hz, 2H, ArH), 7.58 (tt, J=1.5, 6.6 Hz, 1H, ArH), 7.45 (tt, J=1.2, 6.9 Hz, 2H, ArH), 7.24-7.08 (m, 3H, ArH, NCH), 6.91 (dt, J=0.9, 7.2 Hz, 1H, ArH), 4.74 (dd, J=4.2, 10.5 Hz, 1H, CH2O), 4.52-4.43 (m, 1H, ArCH), 4.32 (dd, J=8.4, 10.8 Hz, 1H, CH2O), 3.05 (ddd, J=2.1, 6.9, 16.8 Hz, 1H, CH2CO); 2.95 (ddd, J=2.1, 7.8, 16.8 Hz, 1H, CH2CO), 2.82 (s, 3H, ArCH3); 13C NMR (75 MHz, CDCl3) δ 201.3, 166.3,136.5, 133.2, 130.5, 130.0, 129.7, 128.5, 125.1, 122.6, 122.1, 121.7, 115.8, 109.4, 68.9, 47.8, 31.7, 21.0; HRMS (CI) exact mass calcd for (C20H19NO3) requires m/z 321.1365, found m/z 321.1353. [α]D=−26.6 (c=1.0, CHCl3). The enantiomeric ratio was determined by HPLC analysis of the alcohol, obtained by NaBH4 reduction of the aldehyde, using a Chiracel AD and AD guard column (10:90 ethanol/hexanes, 1 mL/min); S isomer tr=47.8 min and R isomer tr=42.4 min.

Workup

  1. customPrepared
  2. customto provide

Sources & evidence

ORD record
ord-045769d0e2874a5d9c28573ae2d64aab
Source dataset
uspto-grants-2004_08
Patent number
US06784323B2

Reaction notes

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