Stannane, tributyl(1-ethoxyethenyl)- → 4-(3-chloro-5-(1-ethoxyvinyl)pyridin-4-ylamino)-8-(cyclopentyloxy)-7-methoxy-2H-chromen-2-one

HRID 20644

Reaction equation

HRID 20644 reaction equation
Br[C:2]1[CH:3]=[N:4][CH:5]=[C:6]([Cl:28])[C:7]=1[NH:8][C:9]1[C:18]2[C:13](=[C:14]([O:21][CH:22]3[CH2:26][CH2:25][CH2:24][CH2:23]3)[C:15]([O:19][CH3:20])=[CH:16][CH:17]=2)[O:12][C:11](=[O:27])[CH:10]=1.C([Sn](CCCC)(CCCC)[C:34]([O:36][CH2:37][CH3:38])=[CH2:35])CCC>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1(C)C=CC=CC=1>[Cl:28][C:6]1[CH:5]=[N:4][CH:3]=[C:2]([C:34]([O:36][CH2:37][CH3:38])=[CH2:35])[C:7]=1[NH:8][C:9]1[C:18]2[C:13](=[C:14]([O:21][CH:22]3[CH2:26][CH2:25][CH2:24][CH2:23]3)[C:15]([O:19][CH3:20])=[CH:16][CH:17]=2)[O:12][C:11](=[O:27])[CH:10]=1

Participants

5

Reactant 2

HCID 619414Stannane, tributyl(1-ethoxyethenyl)-HCID 248494324-(3-bromo-5-chloropyridin-4-ylamino)-8-(cyclopentyloxy)-7-methoxy-2H-chromen-2-one

Product 1

HCID 248494754-(3-chloro-5-(1-ethoxyvinyl)pyridin-4-ylamino)-8-(cyclopentyloxy)-7-methoxy-2H-chromen-2-one

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4-(3-bromo-5-chloropyridin-4-ylamino)-8-(cyclopentyloxy)-7-methoxy-2H-chromen-2-one (0.206 g, 0.441 mmol, Example 11), PdCl2(PPh3)2 (31 mg, 0.044 mmol), tributyl(1-ethoxyvinyl)tin (0.20 mL, 0.57 mmol), and toluene (5 mL) was heated at 80° C. under N2 for 4 h. After allowing to cool to rt, the mixture was filtered through Celite and washed with EtOAc. The filtrate was washed with aqueous KF, dried, filtered, concentrated, and purified by silica gel chromatography (0→50% EtOAc/hexanes) to give 4-(3-chloro-5-(1-ethoxyvinyl)pyridin-4-ylamino)-8-(cyclopentyloxy)-7-methoxy-2H-chromen-2-one: 1H NMR (400 MHz, DMSO-d6): δ 9.19 (s, 1H), 8.80 (s, 1H), 8.65 (s, 1H), 7.94 (d, 1H), 7.16 (d, 1H), 4.83 (m, 1H), 4.53 (m, 2H), 4.41 (d, 1H), 3.90 (s, 3H), 3.61 (m, 2H), 1.85-1.52 (m, 8H), 0.89 (t, 3H); MS (ESI): 457.1.

Workup

  1. temperatureto cool to rt
  2. filtrationthe mixture was filtered through Celite
  3. washwashed with EtOAc
  4. washThe filtrate was washed with aqueous KF
  5. customdried
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified by silica gel chromatography (0→50% EtOAc/hexanes)

Sources & evidence

ORD record
ord-ddc9b5bf070a45d4b17954f779411030
Source dataset
uspto-grants-2010_06
Patent number
US07745646B2

Linked notes

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