Iodoethane → Methyl 2-(3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)butanoate

HRID 1930143Notes

Reaction equation

HRID 1930143 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[Cl:11][C:12]1[CH:13]=[C:14]([CH2:27][C:28]([O:30][CH3:31])=[O:29])[CH:15]=[CH:16][C:17]=1[B:18]1[O:22][C:21]([CH3:24])([CH3:23])[C:20]([CH3:26])([CH3:25])[O:19]1.I[CH2:33][CH3:34].[Cl-].[NH4+]>C1COCC1.[Ag].C(OCC)(=O)C>[Cl:11][C:12]1[CH:13]=[C:14]([CH:27]([CH2:33][CH3:34])[C:28]([O:30][CH3:31])=[O:29])[CH:15]=[CH:16][C:17]=1[B:18]1[O:22][C:21]([CH3:23])([CH3:24])[C:20]([CH3:25])([CH3:26])[O:19]1

Participants

8

Reactant 4

HCID 6340IodoethaneHCID 25517Ammonium ChlorideHCID 2733832Lithium HexamethyldisilazideHCID 58464478Benzeneacetic acid, 3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-, methyl ester2×

Product 1

HCID 59627654Methyl 2-(3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)butanoateYield 62.9%

Reagents, catalysts & solvents 3

HCID 23954SilverCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Lithium bis(trimethylsilyl)amide (3.86 mL, 3.86 mmol) was added to methyl 2-(3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)acetate (Intermediate 2-7; 1 g, 3.22 mmol) in THF (10 mL) cooled to 0° C. under nitrogen. The resulting solution was stirred at 0° C. for 30 minutes. Iodoethane, stabilized with silver (0.258 mL, 3.22 mmol), was added and the reaction stirred for 30 minutes. Ammonium chloride (satd) (25 mL) added with vigorous stirring, ethyl acetate (50 mL) added and the organic phase separated, washed with water (25 mL) and saturated brine (25 mL). The organic layer was dried over MgSO4, filtered and evaporated to afford crude product. The crude product was purified by flash silica chromatography, elution gradient 0 to 10% EtOAc in isohexane. Pure fractions were evaporated to dryness to afford methyl 2-(3-chloro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)butanoate (0.686 g, 62.9%) as a colourless oil.

Workup

  1. additionwas added
  2. stirringthe reaction stirred for 30 minutes
  3. additionadded
  4. customthe organic phase separated
  5. washwashed with water (25 mL) and saturated brine (25 mL)
  6. dry with materialThe organic layer was dried over MgSO4
  7. filtrationfiltered
  8. customevaporated
  9. customto afford crude product
  10. customThe crude product was purified by flash silica chromatography, elution gradient 0 to 10% EtOAc in isohexane
  11. customPure fractions were evaporated to dryness

Sources & evidence

ORD record
ord-892af2e11a214dd999708109a5814543
Source dataset
uspto-grants-2012_05
Patent number
US08188092B2

Reaction notes

Loading…