3-Buten-2-one,4-(4-bromophenyl)- → HCID 68433579, compound

HRID 2242645Notes

Reaction equation

HRID 2242645 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[CH:9]/[C:10](=[O:12])[CH3:11])=[CH:4][CH:3]=1.[B]1OC2C(=CC=CC=2)O1>C1(C)C=CC=CC=1.B1(C)OC(C2C=CC=CC=2)(C2C=CC=CC=2)[C@@H]2N1CCC2.O>[Br:1][C:2]1[CH:3]=[CH:4][C:5](/[CH:8]=[CH:9]/[C@@H:10]([OH:12])[CH3:11])=[CH:6][CH:7]=1

Participants

6

Reactant 2

HCID 9689183-Buten-2-one,4-(4-bromophenyl)-HCID 6327445Benzcatechinborane

Product 1

HCID 68433579HCID 68433579, compound

Reagents, catalysts & solvents 3

HCID 9838490(R)-2-Methyl-CBS-oxazaborolidineCatalystHCID 962WaterSolventHCID 1140TolueneSolvent2×

Conditions

Temperature
-78 °C

Procedure

To 5.55 g (24.7 mmol) of the ketone from Step A dissolved in 100 mL of toluene was added 3.7 mL (3.7 mmol, 1M in toluene) of (R)-2-methyl-CBS-oxazaborolidine catalyst and the resultant mixture was stirred at ambient temperature for 15 min. The mixture was cooled to −78° C. and 4.0 mL (37.1 mmol) of catecholborane in 30 mL of toluene was added dropwise over 30 min. After the addition, the slurry was stirred at −78° C. for 60 min while slowly turning homogeneous. The solution was then stirred at −78° C. an additional 4 h (reaction time varies from 4-24 h) until TLC revealed complete disappearance of starting material. Next, the reaction mixture was diluted with 100 mL of water and the resultant mixture was extracted with three 100-mL portions of diethyl ether. The organic phases were then combined and washed with two 100-mL portions of 1N aqueous sodium hydroxide solution, two 100-mL portions of 5% hydrochloric acid solution, one 100-mL portion of saturated aqueous brine, dried over magnesium sulfate, filtered, and evaporated in vacuo to yield the crude waxy solid. The crude material was then purified by flash chromatography on a Biotage® system (silica gel, 0 to 20% ethyl acetate/hexanes gradient) to give the alcohol as a colorless crystalline solid. This compound was recrystallized in hexanes to yield the alcohol as colorless crystals (96% ee by Mosher ester analysis). LC/MS 209.0 (M-water+1), 211.0 (M-water+3).

Workup

  1. additionAfter the addition
  2. stirringThe solution was then stirred at −78° C. an additional 4 h
  3. custom(reaction time varies from 4-24 h) until TLC
  4. extractionthe resultant mixture was extracted with three 100-mL portions of diethyl ether
  5. washwashed with two 100-mL portions of 1N aqueous sodium hydroxide solution, two 100-mL portions of 5% hydrochloric acid solution, one 100-mL portion of saturated aqueous brine
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. customto yield the crude waxy solid
  10. customThe crude material was then purified by flash chromatography on a Biotage® system (silica gel, 0 to 20% ethyl acetate/hexanes gradient)

Sources & evidence

ORD record
ord-0db71b35b3744afd9eb754d334aa5e2f
Source dataset
uspto-grants-2010_03
Patent number
US07671073B2

Reaction notes

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