Participants
| Role | Name | HCID | Charge |
|---|
| Reactant | Sodium Carbonate | HCID 10340 | — |
| Reactant | Triphenylphosphine | HCID 11776 | — |
| Reactant | Boronic Acid | HCID 61668 | — |
| Reactant | Toluene water | HCID 22272177 | — |
| Reactant | HCID 68110300 | HCID 68110300 | — |
| Catalyst | palladium(II) acetate | HCID 167845 | — |
| Solvent | Water | HCID 962 | — |
| Product | HCID 68110325 | HCID 68110325 | — |
Reaction Steps
A solution of 4-N-[5-bromo-6-ethylthieno[2,3-d]pyrimidin-4-yl]-1-N,1-N-dimethylcyclohexane-1,4-diamine (1 g, 2.61 mmol, 1.00 equiv) in toluene/H2O (30/10 mL) was added 1-benzofuran-2-yl)boronic acid (970 mg, 5.99 mmol, 2.30 equiv), Pd(OAc)2 (70 mg, 0.31 mmol, 0.12 equiv), PPh3 (240 mg, 0.92 mmol, 0.35 equiv) and sodium carbonate (940 mg, 8.87 mmol, 3.40 equiv) subsequently under nitrogen. The resulting solution was heated to reflux for 4 hr and cooled to room temperature. The resulting solution was diluted with 50 mL of H2O and extracted with 3×80 mL of ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate and concentrated under vacuum. The crude product (500 mg) was purified by Prep-HPLC with the following conditions (SHIMADZU): Column, SunFire Prep C18, 19*150 mm 5 um; mobile phase, water with 0.05% TFA and CH3CN (10% CH3CN up to 30% in 14 min); Flow rate, 20 mL/min; UV detection at 254/220 nm. The product-containing fractions were collected and partially evaporated to remove water and CH3CN under reduced pressure. The residue was neutralized with 2 M aqueous NaOH solution and extracted with DCM, dried over Na2SO4 and concentrated under reduced pressure to give the corresponding 4-N-[5-(1-benzofuran-2-yl)-6-ethylthieno[2,3-d]pyrimidin-4-yl]-1-N,1-N-dimethylcyclohexane-1,4-diamine (130 mg) as yellow semi-solid. MS (ES, m/z): 421 [M+H]+. 1H NMR (300 Hz, CDCl3): δ 8.45 (s, 1H), 7.71-7.68 (d, 1H), 7.57-7.54 (d, 1H), 7.45-7.36 (m, 2H), 6.85 (s, 1H), 5.44-5.42 (d, 1H), 4.03-3.93 (m, 1H) 2.99-2.91 (dd, 2H), 2.30 (s, 6H) 2.23-2.10 (m, 4H), 2.02-1.85 (m, 3H), 1.46-1.31 (m, 5H), 0.92-0.89 (dd, 2H).
Provenance & Evidence
| DOI | 10.6084/m9.figshare.5104873.v1 |
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| Patent number | US08703941B2 |
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| Source dataset | uspto-grants-2014_04 |
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| ORD ID | ord-91d7aee78d3c460c88752610fb019958 |
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| Source note | uspto-grants-2014_04 |
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