تفاعل #45419

معادلة التفاعل

mixture

7-iodo-3-(4-phenoxyphenyl)thieno[3,2-c]pyridin-4-amine

tert-butyl acrylate

PPh3

Na2CO3

→

desired product

المردود 76.0%

tert-butyl (2E)-3-[4-amino-3-(4-phenoxyphenyl)thieno[3,2-c]pyridin-7-yl]acrylate

المردود 76.0%

المذيبات

DMF

ظروف التفاعل

المعالجة

1. 1
   تركيزThe mixture was concentrated to half its original volume
2. 2
   workup.ADDITIONpoured into 10% NaCl (300 mL)
3. 3
   استخلاصThe product was extracted with ethyl acetate (3×70 mL)
4. 4
   غسيلThe combined organic extracts were washed with brine
5. 5
   تجفيفdried (MgSO4)
6. 6
   ترشيحfiltered
7. 7
   تركيزconcentrated
8. 8
   workup.DISSOLUTIONThe residue was dissolved in dichloromethane (300 mL)
9. 9
   workup.ADDITIONtreated with silica gel (25 g)
10. 10
    تركيزconcentrated
11. 11
    أخرىchromatographed with ethyl acetate/heptane (1:6)

الإجراء التجريبي

A mixture of Example 221A (2 g, 4.5 mmol), tert-butyl acrylate (1.3 mL, 8.8 mmol), Pd(OAc)2 (100 mg, 0.44 mmol), PPh3 (236 mg, 0.89 mmol), Na2CO3 (0.95 g, 8.9 mmol), and DMF (40 mL) was stirred for 18 hours at 80° C. under a nitrogen atmosphere. The mixture was concentrated to half its original volume and poured into 10% NaCl (300 mL). The product was extracted with ethyl acetate (3×70 mL). The combined organic extracts were washed with brine, dried (MgSO4), filtered, and concentrated. The residue was dissolved in dichloromethane (300 mL), treated with silica gel (25 g), and concentrated. The preabsorbed silica gel was subsequently transferred to a silica gel (200 g) column and chromatographed with ethyl acetate/heptane (1:6) to provide 1.52 g (76%) of the desired product. 1H NMR (CD2Cl2, 400 MHz) δ 8.13 (s, 1H), 7.78 (d, 1H), 7.49-7.43 (m, 4H), 7.32 (s, 1H), 7.22 (t, 1H), 7.15 (d, 4H), 6.46 (d, 1H), 5.18 (br s, 2H), 1.59 (s, 9H); 13C NMR (CD2Cl2, 100 MHz) δ 166.8, 158.5, 156.8, 155.5, 147.1, 146.9, 139.8, 137.5, 131.3, 130.7, 130.4, 124.4, 123.8, 119.9, 119.7, 118.8, 118.7, 117.2, 80.6, 28.4.

المصدر