Cesium carbonate → HCID 89183375, compound

HRID 877013Notes

Reaction equation

HRID 877013 reaction equation
Br[C:2]1[C:10]2[C:9](=[O:11])[N:8]([CH3:12])[C:7](=[O:13])[N:6]([CH3:14])[C:5]=2[S:4][C:3]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16].C(=O)([O-])[O-].[Cs+].[Cs+].[CH2:26](B1OC(C)(C)C(C)(C)O1)[CH:27]=[CH2:28]>C1COCC1.O.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>[CH2:28]([C:2]1[C:10]2[C:9](=[O:11])[N:8]([CH3:12])[C:7](=[O:13])[N:6]([CH3:14])[C:5]=2[S:4][C:3]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16])[CH:27]=[CH2:26]

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 27631714,4,5,5-Tetramethyl-2-(prop-2-en-1-yl)-1,3,2-dioxaborolaneHCID 71007968HCID 71007968, compound

Product 1

HCID 89183375HCID 89183375, compound

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of Step 5 intermediate (24.5 g, 70.60 mmol) in dry THF (350 ml) was added cesium carbonate (46.0 g, 141.20 mmol) and allyl boronic acid pinacol ester (23.8 ml, 127.08 mmol) under nitrogen atmosphere and the mixture was degassed for 10 min. Tetrakis(triphenylphosphine)palladium(0) (8.1 g, 7.06 mmol) was added and the reaction was refluxed for 24 h under nitrogen atmosphere. The reaction mixture was diluted with water (250 ml) and extracted with ethyl acetate (3×100 ml). The combined extracts were concentrated and the residue obtained was purified by silica gel column chromatography using 5% ethyl acetate in pet ether to give 4.62 g of the product as an off-white solid; 1H NMR (300 MHz, CDCl3) δ 1.39 (t, J=7.2 Hz, 3H), 3.41 (s, 3H), 3.56 (s, 3H), 4.18-4.24 (m, 2H), 4.31-4.40 (m, 2H), 4.99-5.15 (m, 2H), 5.95-6.03 (m, 1H).

Workup

  1. customthe mixture was degassed for 10 min
  2. temperaturethe reaction was refluxed for 24 h under nitrogen atmosphere
  3. extractionextracted with ethyl acetate (3×100 ml)
  4. concentrationThe combined extracts were concentrated
  5. customthe residue obtained
  6. customwas purified by silica gel column chromatography

Sources & evidence

ORD record
ord-abe61bd0756e46ee85400acf2857fad0
Source dataset
uspto-grants-2015_03
Patent number
US08987278B2

Reaction notes

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