Cyclopropylacetylene → HCID 86724301, compound

HRID 594899Notes

Reaction equation

HRID 594899 reaction equation
C(OC([N:8]([C:16]1[O:17][CH2:18][C:19]2([C:32]3([CH2:35][O:34][CH2:33]3)[C:28]3([CH2:31][CH2:30][CH2:29]3)[O:27][C:26]3[C:21]2=[CH:22][C:23]([C:36]2[CH:37]=[N:38][CH:39]=[C:40](Br)[CH:41]=2)=[CH:24][CH:25]=3)[N:20]=1)C(OC(C)(C)C)=O)=O)(C)(C)C.[C:43]([CH:45]1[CH2:47][CH2:46]1)#[CH:44]>CCN(CC)CC.C1(C)C=CC=CC=1.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.[Cu]I>[CH:45]1([C:43]#[C:44][C:40]2[CH:41]=[C:36]([C:23]3[CH:22]=[C:21]4[C:19]5([CH2:18][O:17][C:16]([NH2:8])=[N:20]5)[C:32]5([CH2:33][O:34][CH2:35]5)[C:28]5([CH2:31][CH2:30][CH2:29]5)[O:27][C:26]4=[CH:25][CH:24]=3)[CH:37]=[N:38][CH:39]=2)[CH2:47][CH2:46]1

Participants

7

Reactant 2

HCID 138823CyclopropylacetyleneHCID 86724302HCID 86724302, compound

Product 1

HCID 86724301HCID 86724301, compoundYield 15.6%

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolventHCID 8471TriethylamineSolvent

Procedure

To a stirred solution of di-tert-butyl[6′-(5-bromopyridin-3-yl)trispiro[cyclobutane-1,2′-chromene-4′,4″-[1,3]oxazole-3′,3′″-oxetan]-2″-yl]imidodicarbonate (48 mg, 0.075 mmol) in Et3N (0.67 ml) were added ethynylcyclopropane (0.063 mL, 0.75 mmol), PdCl2(PPh3)2 (10 mg, 0.015 mmol) and CuI (5.7 mg, 0.030 mmol) at room temperature and the mixture was sealed and irradiated with microwave at 150° C. for 1 hour. To this mixture was added activated carbon (ca. 100 mg) and the mixture was stirred for 1 hour to remove palladium residues. The mixture was passed through a pad of Celite. The filtrate was evaporated to give a residue. To the solution of the residue in toluene (3 ml) was added silica gel (500 mg) and the mixture was refluxed for 2 hours. The mixture was passed through a pad of Celite and the filtrate was evaporated to give a crude product, which was purified with column chromatography (MeOH in CHCl3=0 to 10%) to give 6′-[5-(cyclopropylethynyl)pyridin-3-yl]trispiro[cyclobutane-1,2′chromene-4′,4″-[1,3]oxazole-3′,3′″-oxetan]-2″-amine (5 mg).

Workup

  1. customthe mixture was sealed
  2. customirradiated with microwave at 150° C. for 1 hour
  3. additionTo this mixture was added activated carbon (ca. 100 mg)
  4. customto remove palladium residues
  5. customThe filtrate was evaporated
  6. customto give a residue
  7. temperaturethe mixture was refluxed for 2 hours
  8. customthe filtrate was evaporated
  9. customto give a crude product, which
  10. customwas purified with column chromatography (MeOH in CHCl3=0 to 10%)

Sources & evidence

ORD record
ord-92a401aa5ccd4a7fbc3f8682b6b963b2
Source dataset
uspto-grants-2016_01
Patent number
US09242973B2

Reaction notes

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