Allyltributylstannane → 5-allyl-2,2-dimethyl-benzo[1,3]dioxin-4-one

HRID 1582237Notes

Reaction equation

HRID 1582237 reaction equation
[CH3:1][C:2]1([CH3:20])[O:7][C:6](=[O:8])[C:5]2[C:9](S(C(F)(F)F)(=O)=O)=[CH:10][CH:11]=[CH:12][C:4]=2[O:3]1.[Li+].[Cl-].[CH2:23]([Sn](CCCC)(CCCC)CCCC)[CH:24]=[CH2:25].[F-].[K+]>CC1CNC(=O)C1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1C=CC=C1P(C1OC=CC=1)C1OC=CC=1>[CH2:25]([C:9]1[C:5]2[C:6](=[O:8])[O:7][C:2]([CH3:20])([CH3:1])[O:3][C:4]=2[CH:12]=[CH:11][CH:10]=1)[CH:24]=[CH2:23]

Participants

8

Reactant 4

HCID 90628AllyltributylstannaneHCID 433294Lithium ChlorideHCID 522689Potassium FluorideHCID 22336191HCID 22336191, compound

Product 1

HCID 111486725-allyl-2,2-dimethyl-benzo[1,3]dioxin-4-oneYield 97.2%

Reagents, catalysts & solvents 3

HCID 521585Tris(furan-2-yl)phosphaneCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 5339204-methylpyrrolidin-2-oneSolvent

Procedure

To a stirred suspension of 2,2-dimethyl-5-(trifluoromethanesulfonyl)benzo[1,3]dioxin-4-one (iii) (2.0 g, 6.13 mmol), anhydrous LiCl (0.8 g, 18.4 mmol), Pd2(dba)3 (112 mg, 0.12 mmol), and tri-(2-furyl)phosphine (115 mg, 0.49 mmol) in 4-methyl-2-pyrrolidinone (10 mL) was added allyltributyltin (2.35 mL, 7.36 mmol). After stirring for 48 h at rt, saturated aqueous KF (20 mL) was added and an extraction was performed with Et2O (3×). The combined organics were dried over MgSO4, concentrated in vacuo and the residue was purified by FC (4% EtOAc/hexanes) to give 1.3 g of 5-allyl-2,2-dimethyl-benzo[1,3]dioxin-4-one (iv) which was slightly impure.

Workup

  1. extractionan extraction
  2. dry with materialThe combined organics were dried over MgSO4
  3. concentrationconcentrated in vacuo
  4. customthe residue was purified by FC (4% EtOAc/hexanes)

Sources & evidence

ORD record
ord-232c9d3ec92b40cc98b4b7cf8096c00e
Source dataset
uspto-grants-2004_05
Patent number
US06734209B2

Reaction notes

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