2,4-Dinitrobenzoic acid → HCID 86588407, compound

HRID 1837856Notes

Reaction equation

HRID 1837856 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.[Cl:14][C:15]1[CH:23]=[C:22]2[C:18]([CH:19]=[CH:20][NH:21]2)=[CH:17][CH:16]=1.[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:19]1[C:18]2[C:22](=[CH:23][C:15]([Cl:14])=[CH:16][CH:17]=2)[NH:21][CH:20]=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 871116-ChloroindoleHCID 103098345-Benzyl-2-tert-butyl-3-methyl-4-imidazolidinone, (2S,5S)-HCID 566166104-(Benzyloxy)but-2-enal

Product 1

HCID 86588407HCID 86588407, compoundYield 75.7%

Reagents, catalysts & solvents 2

HCID 3776IsopropanolSolventHCID 6344DichloromethaneSolvent2×

Procedure

Prepared according to the general procedure from 4-benzyloxy-but-2-enal (143 mg, 0.750 mmol), 6-chloro-1H-indole (75.8, 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 12.75 h to provide, after silica gel chromatography (CH2Cl2), the title compound as a colorless oil (124 mg, 73% yield, 97% ee) after silica gel chromatography in CH2Cl2. IR (film) 3383, 2953, 2930, 2834, 2734, 1718, 1623, 1603, 1548, 1453, 1403, 1378, 1273, 1184, 1104, 1069, 1019, 909, 804, 774, 714 cm−1; 1HNMR (300 MHz, CDCl3) δ 9.77 (dd, J=1.8, 1.8 Hz, 1H, CHO), 8.15 (s, 1H, NH), 8.02-7.99 (m, 2H, ArH), 7.65 (dd, J=0.6, 8.7 Hz, 1H, ArH), 7.58 (tt, J=1.5, 6.6 Hz, 1H, ArH), 7.48-7.42 (m, 2H, ArH), 7.37 (d, J=1.8 Hz, 1H NCH), 7.12 (dt, J=2.1, 8.7 Hz, 2H, ArH), 4.70 (dd, J=5.1, 10.8 Hz, 1H, CH2O), 4.42 (dd, J=8.4, 11.1 Hz, 1H, CH2O), 4.08 (m, 1H, ArCH), 3.06 (ddd, J=1.8, 6.3. 16.8 Hz, 1H, CH2CO); 2.95 (ddd, J=2.1, 7.8, 16.5 Hz, 1H, CH2CO); 13C NMR (75 MHz, CDCl3) δ 200.9, 166.5, 136.7, 135.4, 133.2, 129.9, 129.6, 128.5. 125.1, 122.3, 120.7, 119.8, 115.0, 111.4, 67.8, 46.5, 31.0; HRMS (CI) exact mass calcd for (C19H16ClNO3) requires m/z 341.0819, found m/z 341.0814.[α]D=−3.3 (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=38.8 min and R isomer tr=43.3 min.

Workup

  1. customPrepared
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Sources & evidence

ORD record
ord-c27c0aefc98f469681ddce3902e5d94e
Source dataset
uspto-grants-2004_08
Patent number
US06784323B2

Reaction notes

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