Quinone → HCID 22989530, compound

HRID 1168703Notes

Reaction equation

HRID 1168703 reaction equation
C1(=O)C=CC(=O)C=C1.[Cl-].[Li+].[CH3:11][C:12]1[CH:17]=[CH:16][C:15]([S:18]([O:21][CH2:22][C@@H:23]2[O:28][C:27]3[C:29]([CH2:34][CH:35]=[CH2:36])=[C:30]([NH2:33])[CH:31]=[CH:32][C:26]=3[O:25][CH2:24]2)(=[O:20])=[O:19])=[CH:14][CH:13]=1>O1CCCC1.C(OCC)(=O)C>[CH3:11][C:12]1[CH:17]=[CH:16][C:15]([S:18]([O:21][CH2:22][CH:23]2[O:28][C:27]3=[C:29]4[C:30](=[CH:31][CH:32]=[C:26]3[O:25][CH2:24]2)[NH:33][C:35]([CH3:36])=[CH:34]4)(=[O:20])=[O:19])=[CH:14][CH:13]=1

Participants

6

Reactant 3

HCID 4650QuinoneHCID 433294Lithium ChlorideHCID 21136155HCID 21136155, compound

Product 1

HCID 22989530HCID 22989530, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Bis-acetonitrile (II) chloride (0.153 g, 0.60 mmole), 1,4-benzoquinone (0.64 g, 6.0 mmole) and lithium chloride (2.5 g, 60 mmole) were combined in 85 mL of tetrahydrofuran and the mixture stirred under argon for 5 minutes. A solution of (2R)-[8-allyl-7-amino-2,3-dihydro-1,4-benzodioxin-2-yl]methyl 4-methylbenzene-sulfonate (2.2 g, 5.9 mmole) in 25 mL of tetrahydrofuran was added and the mixture stirred for 48 hours at room temperature. The mixture was then diluted with 300 mL of ethyl acetate and washed with 200 mL portions of 1 N aqueous HCl, saturated aqueous sodium bicarbonate and brine, dried over magnesium sulfate, filtered and concentrated in vacuum. Column chromatography on silica gel with methylene chloride as eluant gave 1.1 g of the (R)-enantiomer of the title compound as a gray foam. 1H-NMR (CDCl3): doublet 7.8 δ (2H); broad singlet 7.75 δ (1H); doublet 7.3 δ (2H); doublet 6.75 δ (1H); doublet 6.63 δ (1H); singlet 6.1 δ (1H); multiplet 4.5 δ (1H); multiplet 4.25 δ (3H); doublet of doublets 4.07 δ (1H); singlet 2.43 δ (3H); singlet 2.40 δ (3H).

Workup

  1. stirringthe mixture stirred for 48 hours at room temperature
  2. washwashed with 200 mL portions of 1 N aqueous HCl, saturated aqueous sodium bicarbonate and brine
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuum

Sources & evidence

ORD record
ord-823f34f54fd6403d80de90511daf424e
Source dataset
uspto-grants-2003_09
Patent number
US06627639B2

Reaction notes

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