Water → methyl 2-(tert-butoxy)-2-[2-(3,4-dihydro-2H-1-benzopyran-6-yl)-1-benzothiophen-3-yl]acetate

HRID 590965Notes

Reaction equation

HRID 590965 reaction equation
Br[C:2]1[S:3][C:4]2[CH:20]=[CH:19][CH:18]=[CH:17][C:5]=2[C:6]=1[CH:7]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])[C:8]([O:10][CH3:11])=[O:9].C(=O)([O-])[O-].[Na+].[Na+].O.CC1(C)C(C)(C)OB([C:36]2[CH:37]=[C:38]3[C:43](=[CH:44][CH:45]=2)[O:42][CH2:41][CH2:40][CH2:39]3)O1>CN(C)C=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[C:13]([O:12][CH:7]([C:6]1[C:5]2[CH:17]=[CH:18][CH:19]=[CH:20][C:4]=2[S:3][C:2]=1[C:36]1[CH:45]=[CH:44][C:43]2[O:42][CH2:41][CH2:40][CH2:39][C:38]=2[CH:37]=1)[C:8]([O:10][CH3:11])=[O:9])([CH3:16])([CH3:15])[CH3:14]

Participants

7

Reactant 4

HCID 962Water2×HCID 10340Sodium CarbonateHCID 438110342-(3,4-dihydro-2H-1-benzopyran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 70813729Methyl 2-(2-bromo-1-benzothiophen-3-yl)-2-(tert-butoxy)acetate

Product 1

HCID 70813776methyl 2-(tert-butoxy)-2-[2-(3,4-dihydro-2H-1-benzopyran-6-yl)-1-benzothiophen-3-yl]acetateYield 55.5%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of methyl 2-(2-bromo-1-benzothiophen-3-yl)-2-(tert-butoxy)acetate (4c) (40 mg, 0.11 mmol) in N,N-dimethylformamide (2 mL) were successively added sodium carbonate (13 mg, 0.12 mmol), water (500 μL), palladium tetrakis(triphenylphosphine) (18.3 mg, 0.016 mmol) and 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)chroman (29 mg, 0.11 mmol). The mixture was heated at 100° C. for 2 hours. After cooling to room temperature, water (10 mL) was added. The aqueous layer was extracted with ethyl acetate (2×10 mL). The organic layer was washed with brine (10 mL), dried over sodium sulfate, filtered and evaporated to dryness. The residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 90/10) to afford the desired product (4d) as a white solid (25 mg, 0.061 mmol, 55%).

Workup

  1. temperatureAfter cooling to room temperature
  2. extractionThe aqueous layer was extracted with ethyl acetate (2×10 mL)
  3. washThe organic layer was washed with brine (10 mL)
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. customevaporated to dryness
  7. customThe residue was purified by flash chromatography on silica gel (cyclohexane/ethyl acetate 90/10)

Sources & evidence

ORD record
ord-0aaf0e1a204a43dbb719e44fcf4c50bd
Source dataset
uspto-grants-2016_01
Patent number
US09238026B2

Reaction notes

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