Ethanol → HCID 67076937, compound

HRID 899434Notes

Reaction equation

HRID 899434 reaction equation
[C:1]1(C)C=CC=CC=1.C(O)C.C(OB(C=C)OCCCC)CCC.[F:24][C:25]1([F:54])[CH2:53][CH:28]2[CH:29]([C:43]3[CH:48]=[CH:47][C:46]([O:49][CH2:50][O:51][CH3:52])=[CH:45][CH:44]=3)[O:30][C:31]3[C:36]([CH:27]2[CH2:26]1)=[CH:35][C:34]([O:37][CH2:38][O:39][CH3:40])=[CH:33][C:32]=3[C:41]#N>CCOC(C)=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>[F:24][C:25]1([F:54])[CH2:53][CH:28]2[CH:29]([C:43]3[CH:48]=[CH:47][C:46]([O:49][CH2:50][O:51][CH3:52])=[CH:45][CH:44]=3)[O:30][C:31]3[C:32]([CH:41]=[CH2:1])=[CH:33][C:34]([O:37][CH2:38][O:39][CH3:40])=[CH:35][C:36]=3[CH:27]2[CH2:26]1

Participants

7

Reactant 4

HCID 702EthanolHCID 1140TolueneHCID 236543Dibutyl Vinylboronate (stabilized with Phenothiazine)HCID 67076946HCID 67076946, compound

Product 1

HCID 67076937HCID 67076937, compound

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

Add 0.45 mL of toluene, 0.1 mL of absolute ethanol, and vinylboronic acid dibutyl ester (0.030 mL, 0.136 mmol) to a 4 mL vial containing preparation 16 (30 mg, 0.062 mmol) and Pd(PPh3)4 (7 mg, 0.0061 mmol). Bubble nitrogen through the solution for 5 min, seal tightly, and warm to 80° C. with stirring overnight. Dilute the solution with EtOAc and wash with brine. Back extract the aqueous solution with EtOAc. Wash the combined organic solutions with brine, dry over Na2SO4, filter, and concentrate. Adsorb the material to 500 mg of silica gel and purify by silica gel flash chromatography (4 g, 0-20% A/B, A=EtOAc, B=10% CH2Cl2 in hexanes) to afford 12 mg (0.028 mmol, 45%) of preparation 18. 1H NMR (400 MHz, CDCl3) δ 7.38-7.33 (m, 2H), 7.14-7.05 (m, 4H), 6.74 (d, 1H, J=2.6 Hz), 5.77 (dd, 1H, J=1.3, 18.1 Hz), 5.28 (dd, 1H, J=1.3, 12.3 Hz), 5.20 (s, 2H), 5.15 (d, 1H, J=10.1 Hz), 5.13 (d, 1H, J=9.7 Hz), 5.02 (bs, 1H), 3.67 (dt, 1H, J=3.1, 11.0 Hz), 3.50 (s, 1H), 2.89 (m, 1H), 2.74 (m, 1H), 2.30 (m, 1H), 2.17 (m, 1H), 1.86 (m, 1H).

Workup

  1. additionvial containing
  2. customseal tightly
  3. washwash with brine
  4. extractionBack extract the aqueous solution with EtOAc
  5. washWash the combined organic solutions with brine
  6. dry with materialdry over Na2SO4
  7. filtrationfilter
  8. concentrationconcentrate
  9. custompurify by silica gel flash chromatography (4 g, 0-20% A/B
  10. customA=EtOAc, B=10% CH2Cl2 in hexanes) to afford
  11. custom12 mg (0.028 mmol, 45%) of preparation 18

Sources & evidence

ORD record
ord-d716bd3d979d4eef955ee26b2aa26e53
Source dataset
uspto-grants-2008_04
Patent number
US07354951B2

Reaction notes

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