1-Chloro-2-nitrobenzene → HCID 23587460, compound

HRID 1500264Notes

Reaction equation

HRID 1500264 reaction equation
Cl[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[C:11]([O:15][C:16]([N:18]1[CH2:23][CH:22]=[C:21](B2OC(C)(C)C(C)(C)O2)[CH2:20][CH2:19]1)=[O:17])([CH3:14])([CH3:13])[CH3:12].[O-]P([O-])([O-])=O.[K+].[K+].[K+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1>[C:11]([O:15][C:16]([N:18]1[CH2:19][CH:20]=[C:21]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=2[N+:8]([O-:10])=[O:9])[CH2:22][CH2:23]1)=[O:17])([CH3:14])([CH3:12])[CH3:13]

Participants

6

Reactant 3

HCID 69451-Chloro-2-nitrobenzeneHCID 62657Potassium Phosphate, TribasicHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylate

Product 1

HCID 23587460HCID 23587460, compoundYield 72.3%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylCatalyst

Procedure

1-Chloro-2-nitrobenzene (3.00 mmol, 475 mg), Pd2(DBA)3 (0.060 mmol, 55 mg), S-Phos (0.18 mmol, 75 mg), 4-(4,4,5,5-Tetramethyl-[1,3,2]dioxaborolan-2-yl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester (4.0 mmol, 1.2 g) and K3PO4 (4.5 mmol, 1.0 g) were loaded into a Schlenk tube containing a stir bar. The tube was capped with a rubber septum, evacuated and refilled with nitrogen. Toluene (5 mL) was added through the septum via a syringe and the tube was sealed with a Teflon screw cap under a flow of nitrogen, and put into an oil bath at 100° C. The reaction was allowed to stir at this temperature for about 15 hours, then the reaction mixture was cooled to room temperature and filtered through celite. The filtrate was concentrated in vacuo and the resulting residue was purified using flash column chromatography on silica gel (eluent: 14% EtOAc in Hexane) to provide 4-(2-nitro-phenyl)-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester as a brown solid 660 mg, 72%). 1H NMR (400 MHz, CDCl3) δ 7.90 (dd, J=8.0, 1.6 Hz, 1H), 7.58-7.53 (m, 1H), 7.44-7.39 (m, 1H), 7.30-7.27 (m, 1H), 5.62-5.58 (m, 1H), 4.04-4.01 (m, 2H), 3.64 (t, J=5.2 Hz, 2H), 2.36-2.30 (m, 2H), 1.49 (s, 9H).

Workup

  1. additioncontaining a stir bar
  2. customThe tube was capped with a rubber septum
  3. customevacuated
  4. additionrefilled with nitrogen
  5. additionToluene (5 mL) was added through the septum via a syringe
  6. customthe tube was sealed with a Teflon
  7. customscrew cap under a flow of nitrogen
  8. customput into an oil bath at 100° C
  9. filtrationfiltered through celite
  10. concentrationThe filtrate was concentrated in vacuo
  11. customthe resulting residue was purified

Sources & evidence

ORD record
ord-be40024112834fe29612287b5e0d1c5f
Source dataset
uspto-grants-2015_12
Patent number
US09206142B2

Reaction notes

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