Ethyl Acetate → HCID 86656478, compound

HRID 594178Notes

Reaction equation

HRID 594178 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:9][C@@H:10]3[N:16]([CH:17]=2)[C:15](=[O:18])[C:14]2[CH:19]=[C:20]([O:61][CH3:62])[C:21]([O:23][CH2:24][CH2:25][CH2:26][O:27][C:28]4[C:58]([O:59][CH3:60])=[CH:57][C:31]5[C:32](=[O:56])[N:33]6[CH:48]=[C:47](S(C(F)(F)F)(=O)=O)[CH2:46][C@H:34]6[C:35](=[O:45])[N:36]([CH2:37][O:38][CH2:39][CH2:40][Si:41]([CH3:44])([CH3:43])[CH3:42])[C:30]=5[CH:29]=4)=[CH:22][C:13]=2[N:12]([CH2:63][O:64][CH2:65][CH2:66][Si:67]([CH3:70])([CH3:69])[CH3:68])[C:11]3=[O:71])=[CH:4][CH:3]=1.[CH3:72][O:73][C:74]1[CH:79]=[CH:78][C:77](B(O)O)=[CH:76][CH:75]=1.C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O>C1(C)C=CC=CC=1.CCO.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>[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:9][C@@H:10]3[N:16]([CH:17]=2)[C:15](=[O:18])[C:14]2[CH:19]=[C:20]([O:61][CH3:62])[C:21]([O:23][CH2:24][CH2:25][CH2:26][O:27][C:28]4[C:58]([O:59][CH3:60])=[CH:57][C:31]5[C:32](=[O:56])[N:33]6[CH:48]=[C:47]([C:77]7[CH:78]=[CH:79][C:74]([O:73][CH3:72])=[CH:75][CH:76]=7)[CH2:46][C@H:34]6[C:35](=[O:45])[N:36]([CH2:37][O:38][CH2:39][CH2:40][Si:41]([CH3:44])([CH3:43])[CH3:42])[C:30]=5[CH:29]=4)=[CH:22][C:13]=2[N:12]([CH2:63][O:64][CH2:65][CH2:66][Si:67]([CH3:70])([CH3:69])[CH3:68])[C:11]3=[O:71])=[CH:4][CH:3]=1

Participants

9

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 201262(4-Methoxyphenyl)boronic acidHCID 86656479HCID 86656479, compound

Product 1

HCID 86656478HCID 86656478, compoundYield 193.7%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

Solid Pd(PPh3)4 (10 mg, 8.69 μmol) was added to a stirred solution of the mono-triflate 9 (230 mg, 0.22 mmol) in toluene (3 mL), EtOH (10 mL), with 4-methoxyphenyl boronic acid (43 mg, 0.28 mmol), Na2CO3 (37 mg, 0.35 mmol), in H2O (1.5 mL) at room temperature. The reaction mixture was allowed to stir under a nitrogen atmosphere for 20 h, at which point the reaction was deemed complete as judged by LC/MS and TLC (EtOAc). The solvent was removed by rotary evaporation under reduced pressure in vacuo and the resulting residue partitioned between EtOAc (75 mL) and H2O (75 mL). The aqueous phase was extracted with EtOAc (3×30 mL) and the combined organic layers washed with H2O (30 mL), brine (40 mL), dried (MgSO4), filtered and evaporated to provide the crude product. The crude product was purified by flash chromatography (60% Hexane: 40% EtOAc→80% EtOAc: 20% Hexane) to provide the pure dimer as an orange foam. Removal of the excess eluent under reduced pressure afforded the desired product 10 (434 mg) in 74% yield.

Workup

  1. customThe solvent was removed by rotary evaporation under reduced pressure in vacuo
  2. customthe resulting residue partitioned between EtOAc (75 mL) and H2O (75 mL)
  3. extractionThe aqueous phase was extracted with EtOAc (3×30 mL)
  4. washthe combined organic layers washed with H2O (30 mL), brine (40 mL)
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. customevaporated
  8. customto provide the crude product
  9. customThe crude product was purified by flash chromatography (60% Hexane: 40% EtOAc→80% EtOAc: 20% Hexane)
  10. customto provide the pure dimer as an orange foam
  11. customRemoval of the excess eluent under reduced pressure

Sources & evidence

ORD record
ord-f0f78e5bf64c4181a9f59b2c0f318a57
Source dataset
uspto-grants-2016_01
Patent number
US09242013B2

Reaction notes

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