Pyridine → HCID 11254965, compound

HRID 971173Notes

Reaction equation

HRID 971173 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7](B(O)O)[CH:8]=[CH:9][CH:10]=1)=[O:4].[OH:14][N:15]1[C:19](=[O:20])[C:18]2=[CH:21][CH:22]=[CH:23][CH:24]=[C:17]2[C:16]1=[O:25].N1C=CC=CC=1>[Cu]Cl.ClCCCl>[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]([CH:8]=[CH:9][CH:10]=1)[O:14][N:15]1[C:16](=[O:25])[C:17]2=[CH:24][CH:23]=[CH:22][CH:21]=[C:18]2[C:19]1=[O:20])=[O:4]

Participants

6

Reactant 3

HCID 1049PyridineHCID 10665N-HydroxyphthalimideHCID 27347143-(Methoxycarbonyl)benzeneboronic acid2×

Product 1

HCID 11254965HCID 11254965, compoundYield 46%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 111,2-DichloroethaneSolvent

Procedure

3-Methoxycarbonylphenylboronic acid was subjected to similar coupling procedures with NHP as outlined above (method 1). A 100 mL round bottom flask was charged with N-hydroxyphthalimide (2.19 g, 13.4 mmol), copper (I) chloride (1.34 g, 13.5 mmol), freshly activated 4 Å molecular sieves (˜5 g), and 3-methoxycarbonylphenylboronic acid (4.79 g, 26.6 mmol). 1,2-Dichloroethane (60 mL) was added followed by pyridine (1.20 mL, 14.8 mmol), and the reaction suspension was stirred in an air atmosphere at room temperature. After 4 days, the mixture was adsorbed onto silica gel and concentrated to a powder. Flash chromatographic purification over silica (33-50% gradient EtOAc in hexanes) afforded 13 as a white solid (1.85 g, 46%). 1H-NMR (500 MHz, CDCl3) δ 3.90 (s, 3H), 7.38-7.41 (ddd, J=1.0, 2.5, 8.3 Hz, 1H), 7.44 (t, J=8.3 Hz, 1H), 7.78 (dd, J=1.0, 2.5 Hz, 1H), 7.82-7.86 (m, 3H), 7.92-7.96 (m, 2H); 13C-NMR (125 MHz, CDCl3) δ 52.5, 115.0, 119.3, 124.3, 125.9, 129.0, 130.0, 132.1, 135.2, 159.0, 163.0, 166.2; ESI-MS 298 m/z [MH]+, C16H12NO5 requires 298.

Workup

  1. concentrationconcentrated to a powder
  2. customFlash chromatographic purification over silica (33-50% gradient EtOAc in hexanes)

Sources & evidence

ORD record
ord-beeb530fa0134052add35dd475fd019c
Source dataset
uspto-grants-2007_12
Patent number
US07312361B2

Reaction notes

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