Cesium fluoride → HCID 68863554, compound

HRID 1725923Notes

Reaction equation

HRID 1725923 reaction equation
Br[C:2]1[C:3]([CH3:28])=[C:4]([C:15]([NH:18][S:19]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][N:23]=2)(=[O:21])=[O:20])=[CH:16][CH:17]=1)[C:5]([O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:6].[CH:29](B(OCCCC)OCCCC)=[CH2:30].[F-].[Cs+]>COCCOC.CO.[Cl-].[Na+].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>[CH3:28][C:3]1[C:2]([CH:29]=[CH2:30])=[CH:17][CH:16]=[C:15]([NH:18][S:19]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][N:23]=2)(=[O:21])=[O:20])[C:4]=1[C:5]([O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:6]

Participants

8

Reactant 3

HCID 25953Cesium fluorideHCID 236543Dibutyl Vinylboronate (stabilized with Phenothiazine)HCID 68865807HCID 68865807, compound

Product 1

HCID 68863554HCID 68863554, compoundYield 46.6%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 80711,2-DimethoxyethaneSolventHCID 57417360Sodium chloride; waterSolvent

Conditions

Temperature
80 °C

Procedure

A solution of Example 110A (1.38 g, 3.0 mmol), dibutyl vinylboronate (0.83 g, 4.5 mmol), CsF (1.36 g, 9.0 mmol), and Pd(PPh3)4 (0.17 g, 0.15 mmol) in DME (12 mL) and methanol (6 mL) was purged with argon and stirred at 80° C. for 36 hours. The mixture was treated with brine (30 mL) and extracted with ethyl acetate. The ethyl acetate solution was dried (MgSO4), filtered and concentrated. The residue was purified by flash column chromatography on a silica gel with 30% ethyl acetate/hexanes to provide the desired product (0.57 g, 46.6%). 1H NMR (DMSO-d6) δ 2.12 (s, 3H), 5.26 (s, 2H), 5.34 (d, 1H), 5.65 (d, 1H), 6.86-6.91 (dd, 1H), 6.98 (d, 1H), 7.31-7.47 (m, 6H), 7.65 (m, 1H), 9.87 (d, 1H), 8.04 (dt, 1H), 8.74 (d, 1H), 10.04 (s, 1H); MS (ESI(+)) m/e 409 (M+H)+. Further elution of the column with 5% methanol in ethyl acetate with 0.1% acetic acid provided another white solid (0.125 g) which was identified as Example 172B.

Workup

  1. extractionextracted with ethyl acetate
  2. dry with materialThe ethyl acetate solution was dried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was purified by flash column chromatography on a silica gel with 30% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-05faa888a0194e638917006f6267c345
Source dataset
uspto-grants-2009_02
Patent number
US07491718B2

Reaction notes

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