3-Methoxypropyne → Di-tert-butyl [6'-(3-methoxyprop-1-yn-1-yl)dispiro[1,3-oxazole-4,4'-chromene-3',3''-oxetan]-2-yl]imidodicarbonate

HRID 873711Notes

Reaction equation

HRID 873711 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:31](=[CH:32][CH:33]=1)[O:30][CH2:29][C:25]1([CH2:28][O:27][CH2:26]1)[C:5]12[CH2:9][O:8][C:7]([N:10]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[N:6]1.[CH3:34][O:35][CH2:36][C:37]#[CH:38]>CCN(CC)CC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:34][O:35][CH2:36][C:37]#[C:38][C:2]1[CH:3]=[C:4]2[C:31](=[CH:32][CH:33]=1)[O:30][CH2:29][C:25]1([CH2:28][O:27][CH2:26]1)[C:5]12[CH2:9][O:8][C:7]([N:10]([C:18]([O:20][C:21]([CH3:23])([CH3:22])[CH3:24])=[O:19])[C:11]([O:13][C:14]([CH3:16])([CH3:15])[CH3:17])=[O:12])=[N:6]1

Participants

5

Reactant 2

HCID 693933-MethoxypropyneHCID 86724239Di-tert-butyl (6'-bromodispiro[1,3-oxazole-4,4'-chromene-3',3''-oxetan]-2-yl)imidodicarbonate

Product 1

HCID 86724253Di-tert-butyl [6'-(3-methoxyprop-1-yn-1-yl)dispiro[1,3-oxazole-4,4'-chromene-3',3''-oxetan]-2-yl]imidodicarbonateYield 23.6%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A mixture of di-tert-butyl (6′-bromodispiro[1,3-oxazole-4,4′-chromene-3′,3″-oxetan]-2-yl)imidodicarbonate (150 mg, 0.286 mmol) and 3-methoxyprop-1-yne (0.072 mL, 0.86 mmol) in Et3N (1.5 mL) was purged with argon. To the mixture was added Pd(PPh3)4 (13 mg, 0.011 mmol) and CuBr (4.9 mg, 0.034 mmol), and the mixture was refluxed for 3 hours under an argon atmosphere. The mixture was partitioned between CHCl3 and brine, and filtered through celite. The organic layer of the filtrate was dried over MgSO4, filtered off, and the filtrate was evaporated. Silicagel column chromatography (EtOAc-hexane, a linear gradient of EtOAc from 0 to 25%) afforded di-tert-butyl [6′-(3-methoxyprop-1-yn-1-yl)dispiro[1,3-oxazole-4,4′-chromene-3′,3″-oxetan]-2-yl]imidodicarbonate (34.7 mg).

Workup

  1. customwas purged with argon
  2. temperaturethe mixture was refluxed for 3 hours under an argon atmosphere
  3. customThe mixture was partitioned between CHCl3 and brine
  4. filtrationfiltered through celite
  5. dry with materialThe organic layer of the filtrate was dried over MgSO4
  6. filtrationfiltered off
  7. customthe filtrate was evaporated

Sources & evidence

ORD record
ord-9d845934c82b467b93ef34e06a3b945a
Source dataset
uspto-grants-2015_03
Patent number
US08975415B2

Reaction notes

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