Water → HCID 178489288, compound

HRID 45434Notes

Reaction equation

HRID 45434 reaction equation
Br[C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[C:4](/[C:9](=[N:16]/[C:17]2[C:22]([CH:23]([CH3:25])[CH3:24])=[CH:21][CH:20]=[CH:19][C:18]=2[CH:26]([CH3:28])[CH3:27])/[C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[C:3]=1[OH:29].[Li]CCCC.Br[C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][C:37]=1[O:42][CH3:43].O>C1COCC1.[Cl-].[Cl-].[Zn+2].CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH:23]([C:22]1[CH:21]=[CH:20][CH:19]=[C:18]([CH:26]([CH3:27])[CH3:28])[C:17]=1/[N:16]=[C:9](\[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)/[C:4]1[CH:5]=[C:6]([CH3:8])[CH:7]=[C:2]([C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][C:37]=2[O:42][CH3:43])[C:3]=1[OH:29])([CH3:24])[CH3:25]

Participants

8

Reactant 4

HCID 962WaterHCID 113582-BromoanisoleHCID 178418339ButyllithiumHCID 178422466HCID 178422466, compound

Product 1

HCID 178489288HCID 178489288, compoundYield 26%

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 178418851HCID 178418851, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-100 °C

Procedure

To a solution of 2.25 g (5.0 mmol) of 34 in 20 mL of THF, 4.0 mL (10.0 mmol) of 2.5 M nBuLi in hexanes was added at −80° C. This mixture was stirred for 1 hr, then cooled to −100° C. and 10.8 mL (10.8 mmol) of 1.0 M ZnCl2 in THF was added. The resulting mixture was slowly warmed to ambient temperature, stirred for 30 min, and then 2.82 g (15.0 mmol) of 2-bromoanisole and 0.14 g (0.25 mmol) of Pd(PtBu3)2 was added. This mixture was refluxed for 8 hr, then 5 mL of water was added. The resulting mixture was passed through a short layer of silica gel 60. The silica gel layer was additionally washed with 30 mL of dichloromethane. The combined organic elute was evaporated to dryness. The product was isolated by flash chromatography on silica gel 60 (40-63 um, eluent: from hexanes to hexanes-diethyl ether, 20:1, vol.) to give 0.55 g (26%) of a yellowish solid.

Workup

  1. temperatureThe resulting mixture was slowly warmed to ambient temperature
  2. stirringstirred for 30 min
  3. temperatureThis mixture was refluxed for 8 hr
  4. washThe silica gel layer was additionally washed with 30 mL of dichloromethane
  5. washThe combined organic elute
  6. customwas evaporated to dryness
  7. customThe product was isolated by flash chromatography on silica gel 60 (40-63 um, eluent: from hexanes to hexanes-diethyl ether, 20:1, vol.)

Sources & evidence

ORD record
ord-ba38f7d4036a42b983404df945cc5402
Source dataset
uspto-grants-2013_09
Patent number
US08541521B2

Reaction notes

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