Phenylacetylene → 6-(Phenylethynyl)-2',4',5',6'-tetrahydrospiro[chroman-2,3'-pyran]-4-one

HRID 2096639Notes

Reaction equation

HRID 2096639 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:14](=[CH:15][CH:16]=1)[O:13][C:7]1([CH2:12][CH2:11][CH2:10][O:9][CH2:8]1)[CH2:6][C:5]2=[O:17].[C:18]1([C:24]#[CH:25])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>[Cu]I.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.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:18]1([C:24]#[C:25][C:2]2[CH:3]=[C:4]3[C:14](=[CH:15][CH:16]=2)[O:13][C:7]2([CH2:12][CH2:11][CH2:10][O:9][CH2:8]2)[CH2:6][C:5]3=[O:17])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

6

Reactant 2

HCID 10821PhenylacetyleneHCID 584238236-Bromo-2',4',5',6'-tetrahydrospiro[chroman-2,3'-pyran]-4-one

Product 1

HCID 584246946-(Phenylethynyl)-2',4',5',6'-tetrahydrospiro[chroman-2,3'-pyran]-4-oneYield 90.5%

Reagents, catalysts & solvents 3

HCID 11776TriphenylphosphineCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalyst

Conditions

Temperature
80 °C

Procedure

An oven dried 3-necked round bottom flask equipped with condenser was charged with 6-bromo-2′,4′,5′,6′-tetrahydrospiro[chroman-2,3′-pyran]-4-one (223 mg, 0.75 mmol), TEA (3 mL) and DEA (0.8 mL) under N2 atmosphere. To this solution was added CuI (5.7 mg, 0.03 mmol), PdCl2(PPh3)2 (21 mg, 0.03 mmol) and PPh3 (16 mg, 0.06 mmol). The system was degas once again, then phenylacetylene (0.41 mL, 3.75 mmol) was added and the mixture was heated to 80° C. (oil bath) with stirring. The reaction was evaporated after 12 h and the residue was purified by flash chromatography (12 g silica gel, eluted with EA in hexane in a gradient of 0-25%, v/v) to afford 6-(phenylethynyl)-2′,4′,5′,6′-tetrahydrospiro[chroman-2,3′-pyran]-4-one (216 mg, yield: 90%). MS ESI +ve m/z 319 (M+H)+.

Workup

  1. customAn oven dried 3-necked round bottom flask
  2. customequipped with condenser
  3. customThe system was degas once again
  4. customThe reaction was evaporated after 12 h
  5. customthe residue was purified by flash chromatography (12 g silica gel
  6. washeluted with EA in hexane in a gradient of 0-25%, v/v)

Sources & evidence

ORD record
ord-92f7cb0e938a4b679a98497fc037b1cc
Source dataset
uspto-grants-2013_05
Patent number
US08450308B2

Reaction notes

Loading…