Sodium Hydroxide → HCID 178489280, compound

HRID 1014789Notes

Reaction equation

HRID 1014789 reaction equation
I[C:2]1[C-:3]([N:7]([CH3:9])[CH3:8])[CH:4]=[CH:5][CH:6]=1.[CH-:10]1[CH:14]=[CH:13][CH:12]=[CH:11]1.[Fe+2:15].[CH3:16][O:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1B(O)O.[OH-].[Na+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.COCCOC>[CH3:16][O:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[C:2]1[C-:3]([N:7]([CH3:9])[CH3:8])[CH:4]=[CH:5][CH:6]=1.[CH-:10]1[CH:14]=[CH:13][CH:12]=[CH:11]1.[Fe+2:15]

Participants

6

Reactant 3

HCID 14798Sodium HydroxideHCID 27339582-Methoxyphenylboronic acidHCID 178482625HCID 178482625, compound

Product 1

HCID 178489280HCID 178489280, compoundYield 88.4%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

Racemic iodide 12i (101 mg, 0.28 mmol), 2-methoxyphenylboronic acid (86 mg, 0.57 mmol) and Pd(PPh3)4 (33 mg, 2.86×10−2 mmol) were added to a dry Schlenk flask, followed by DME (3 mL) and an aqueous solution of 3 M aqueous NaOH (0.24 mL, 0.70 mmol). Argon was bubbled through the resulting mixture for 10 minutes, and the system was heated to reflux for 14 h. The reaction mixture was allowed to cool to room temperature, diluted with Et2O, washed with water (1×5 mL), brine (1×5 mL), dried over Na2SO4, filtered, and all volatiles were removed in vacuo. Gradient flash column chromatography (silica gel, 98:2→95:5 hexane/EtOAc) afforded 57 (83 mg, 87%) as an orange oil that solidified on standing: Rf 0.19 (95:5 hexane/EtOAc); mp 92-93° C. (hexane); IR (KBr) vmax 3082, 2941, 2833, 2776, 1597, 1450, 1411 cm−1; 1H NMR (300 MHz, CDCl3) δ 8.09 (dd, 1H, J=7.5, 1.8 Hz), 7.26 (td, 1H, J=7.8, 1.8 Hz), 7.02 (td, 1H, J=7.5, 0.9 Hz), 6.87 (d, 1H, J=8.4 Hz), 4.27 (t, 1H, J=3.6 Hz), 4.24 (s, 5H), 4.09 (t, 1H, J=2.1 Hz), 4.05 (t, 1H, J=2.7 Hz), 3.79 (s, 3H), 2.47 (s, 6H); 13C NMR (75 MHz, CDCl3) δ 157.5, 132.6, 127.5, 127.0, 120.0, 113.1, 110.5, 75.5, 68.9, 66.8, 62.0, 56.8, 55.6, 44.1; EIMS [m/z (%)] 335 (M+, 100), 229 (24); HRMS (EI) calcd for C19H21NO88Fe: 335.0972. Found 335.0978.

Workup

  1. customArgon was bubbled through the resulting mixture for 10 minutes
  2. temperaturethe system was heated
  3. temperatureto reflux for 14 h
  4. additiondiluted with Et2O
  5. washwashed with water (1×5 mL), brine (1×5 mL)
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. customall volatiles were removed in vacuo

Sources & evidence

ORD record
ord-a81016078a74440e8e1b91fe2c1ee9a7
Source dataset
uspto-grants-2011_07
Patent number
US07982064B2

Reaction notes

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