6-Bromo-2-naphthalenol → Binol

HRID 859086Notes

Reaction equation

HRID 859086 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7]([OH:12])[CH:6]=[CH:5]2>C1C2C(=CC=CC=2)C=CC=1O.C(Cl)(Cl)(Cl)Cl>[CH:2]1[CH:3]=[C:4]2[CH:5]=[CH:6][C:7]([OH:12])=[C:8]([C:8]3[C:9]4[C:4](=[CH:3][CH:2]=[CH:11][CH:10]=4)[CH:5]=[CH:6][C:7]=3[OH:12])[C:9]2=[CH:10][CH:11]=1

Participants

4

Reactant 1

HCID 271446-Bromo-2-naphthalenol

Product 1

HCID 11762BinolYield 99%

Reagents, catalysts & solvents 2

HCID 86632-NaphtholCatalystHCID 5943Carbon TetrachlorideSolvent2×

Procedure

A reaction flask described in example 9 was charged with a solution of catalyst 1c (12.2 mg, 0.02 mmol) in anhydrous CCl4 (1 mL). The solution was stirred for 10 min under an oxygen atmosphere and then treated with a solution of 6-bromo-2-naphthol (44 mg, 0.2 mmol) in anhydrous CCl4 (1 mL) under 0° C. The reaction mixture was stirred at 0° C. until the reaction was complete (monitored by TLC). The crude mixture was concentrated under reduced pressure, and purified by column chromatography (Ethyl acetate/Petroleum ether-⅓) to give (R)-BINOL 3c, Yield 99%. [α]D25=−33.7 (c=0.4 in EtOAc), 1H NMR (300 MHz, CDCl3) δ (ppm) 8.06 (d, J=1.8 Hz, 2H, 2×HC (4)), 7.89 (d, J=9.0 Hz, 2H, 2×HC (5)), 7.37 (d, J=6.9 Hz, 2H, 2×HC (8)), 7.36 (dd, J=9.0 Hz, 1.8 Hz, 2H, 2×HC (7)), 6.96 (d, J=9.0 Hz, 2H, 2×HC (3)), 5.08 (s, 2H, 2×OH). e.e. 90%, and the configuration was R (Kromasil CHI-TBB column, Hexane/propan-2-ol=80: 20; flow rate 1 mL/min; S-isomer, tR 6.68 min and R-isomer, tR 7.51 min).

Workup

  1. customA reaction flask described in example 9
  2. stirringThe reaction mixture was stirred at 0° C. until the reaction
  3. concentrationThe crude mixture was concentrated under reduced pressure
  4. custompurified by column chromatography (Ethyl acetate/Petroleum ether-⅓)

Sources & evidence

ORD record
ord-a4d26601b313438f886c61fbdb2e05ce
Source dataset
uspto-grants-2006_12
Patent number
US07151070B2

Reaction notes

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