Cesium carbonate → HCID 86757573, compound

HRID 428638Notes

Reaction equation

HRID 428638 reaction equation
O[C:2]1[CH:11]=[C:10]2[C:5]([C:6]([CH2:13][CH2:14][CH3:15])=[CH:7][C:8](=[O:12])[O:9]2)=[C:4]2[O:16][C:17]([CH3:21])([CH3:20])[CH:18]=[CH:19][C:3]=12.C(=O)([O-])[O-].[Cs+].[Cs+].C(=O)(OC)[O:29][CH2:30]/[C:31](/[CH3:34])=[CH:32]/[CH3:33]>ClCCl>[CH3:34]/[C:31](=[CH:32]\[CH3:33])/[CH2:30][O:29][C:18]1[C:17]([CH3:20])([CH3:21])[O:16][C:4]2=[C:5]3[C:10](=[CH:11][CH:2]=[C:3]2[CH:19]=1)[O:9][C:8](=[O:12])[CH:7]=[C:6]3[CH2:13][CH2:14][CH3:15]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 5494880HCID 5494880, compoundHCID 10975605HCID 10975605, compound

Product 1

HCID 86757573HCID 86757573, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

5-Hydroxy-2,2-dimethyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one (Example 8, 107 mg, 0.37 mmol) and caesium carbonate (6 mg, 0.019 mmol) were placed in a flask. A solution of (E)-2-methyl-2-butenyl methyl carbonate (108 mg, 0.75 mmol) in dichloromethane (1 ml) was added. Meanwhile, a solution of (−)-1,2-bis-N-[2′-(diphenylphosphino)benzoyl]-11(S),12(S)-diamino-9,10-dihydro-9,10-ethanoanthracene and then dipalladium tris(dibenzylidineacetone)-chloroform adduct (9.5 mg, 0.025 mmol) in dichloromethane (0.5 mmol) was prepared, then added to the reaction. The suspension was heated to reflux for 8 h, then the yellow solution was allowed to cool to room temperature. After adsorption onto silica (500 mg), and elution with heptane-ethyl acetate (9:1), the (S)-allylic ether in a 11:1 mixture with its allylic regioisomer, i.e. (E2-methyl-2-butenyl)oxy-2,2-dimethyl-10-propyl-2H-pyrano[2,3-f]chromen-8-one, was obtained as a yellow oil (132 mg, 100%); enantiomeric excess 94% by chiral HPLC.

Workup

  1. additionadded to the reaction
  2. temperatureThe suspension was heated
  3. temperatureto reflux for 8 h
  4. washAfter adsorption onto silica (500 mg), and elution with heptane-ethyl acetate (9:1)

Sources & evidence

ORD record
ord-9c173e8c173e461c84ad12aa81dedceb
Source dataset
uspto-grants-2001_11
Patent number
US06313320B1

Reaction notes

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