Water → tert-butyl 2-methyl-8-(1-methylethenyl)-2,3-dihydrothieno[2,3-f][1,4]oxazepine-4(5H)-carboxylate

HRID 1404975Notes

Reaction equation

HRID 1404975 reaction equation
Br[C:2]1[C:11]2[O:10][CH:9]([CH3:12])[CH2:8][N:7]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:6][C:5]=2[S:4][CH:3]=1.[C:20](B1OC(C)(C)C(C)(C)O1)([CH3:22])=[CH2:21].C(=O)([O-])[O-].[K+].[K+].O>COCCOC.O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:12][CH:9]1[CH2:8][N:7]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:6][C:5]2[S:4][CH:3]=[C:2]([C:20]([CH3:22])=[CH2:21])[C:11]=2[O:10]1

Participants

7

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolaneHCID 67958981tert-butyl 8-bromo-2-methyl-2,3-dihydrothieno[2,3-f][1,4]oxazepine-4(5H)-carboxylate

Product 1

HCID 67959088tert-butyl 2-methyl-8-(1-methylethenyl)-2,3-dihydrothieno[2,3-f][1,4]oxazepine-4(5H)-carboxylateYield 74%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 18180031Water 1,2-dimethoxyethaneSolvent

Procedure

A mixed solution of tert-butyl 8-bromo-2-methyl-2,3-dihydrothieno[2,3-f][1,4]oxazepine-4(5H)-carboxylate (418 mg) obtained in Example 6, steps 1-6, isopropenylboronic acid pinacol ester (0.293 ml), dichlorobis(triphenylphosphine)palladium (42 mg) and potassium carbonate (498 mg) in DME-water (1:1, 10 mL) was stirred at 85° C. for 1 hr under a nitrogen stream. The reaction solution was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with water and saturated brine, and dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (solvent gradient; 5→12% ethyl acetate/hexane) to give the title compound (274 mg, 74%) as a colorless oil.

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe extract was washed with water and saturated brine
  3. dry with materialdried over magnesium sulfate
  4. customthe solvent was evaporated under reduced pressure
  5. customThe residue was purified by silica gel column chromatography (solvent gradient; 5→12% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-527a103b21c24d45b7c350ea0656ecc2
Source dataset
uspto-grants-2014_12
Patent number
US08916549B2

Reaction notes

Loading…