Sodium Hydroxide → HCID 178482621, compound

HRID 1014790Notes

Reaction equation

HRID 1014790 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].[Br:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=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>[Br:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=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 2773294(2-Bromophenyl)boronic acidHCID 178482625HCID 178482625, compound

Product 1

HCID 178482621HCID 178482621, compoundYield 46.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

Racemic iodide 12i (355 mg, 1.00 mmol), 2-bromophenylboronic acid (210 mg, 1.05 mmol) and Pd(PPh3)4 (115 mg, 0.10 mmol) were added to a dry Schlenk flask, followed by DME (10 mL) and an aqueous solution of 3 M aqueous NaOH (0.50 mL, 1.50 mmol). Argon was bubbled through the resulting mixture for 10 minutes, and the system was heated at reflux for 15 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, 97:3→95:5 t-BuOMe/hexane) afforded 58 (177 mg, 46%) as an orange oil: Rf 0.38 (90:10 hex/EtOAc); IR (KBr, CHCl3) vmax 3091, 2947, 2846, 2783, 1587, 1502, 1485, 1416 cm−1; 1H NMR (300 MHz, CDCl3) δ 8.12 (dd, 1H, J=7.7, 1.5 Hz), 7.26 (dd, 1H, J=8.1, 1.2 Hz), 7.34 (td, 1H, J=7.5, 1.2 Hz), 7.13 (td, 1H, J=7.8, 1.8 Hz), 4.32 (s, 5H), 4.13 (t, 1H, J=1.8 Hz), 4.10-4.05 (m, 2H), 2.41 (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 (%)] 385 (81Br M+, 91), 383 (79Br M+, 100), 182 (62); HRMS (EI) calcd for C18H18N56Fe79Br: 382.9972. Found 382.9974.

Workup

  1. customArgon was bubbled through the resulting mixture for 10 minutes
  2. temperaturethe system was heated
  3. temperatureat reflux for 15 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-840816987a7e4ece98d77f0ea4ebd22d
Source dataset
uspto-grants-2011_07
Patent number
US07982064B2

Reaction notes

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