9-Bromo-9-borabicyclo(3.3.1)nonane → 7-bromo-2-fluoro-3-(tributylstannyl)-5H-chromeno[2,3-b]pyridin-5-one

HRID 335905Notes

Reaction equation

HRID 335905 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([O:31]C)=[C:6]([C:8]([C:10]2[C:11](F)=[N:12][C:13]([F:29])=[C:14]([Sn:16]([CH2:25][CH2:26][CH2:27][CH3:28])([CH2:21][CH2:22][CH2:23][CH3:24])[CH2:17][CH2:18][CH2:19][CH3:20])[CH:15]=2)=[O:9])[CH:7]=1.BrB1C2CCCC1CCC2>C(Cl)Cl>[Br:1][C:2]1[CH:7]=[C:6]2[C:5](=[CH:4][CH:3]=1)[O:31][C:11]1=[N:12][C:13]([F:29])=[C:14]([Sn:16]([CH2:25][CH2:26][CH2:27][CH3:28])([CH2:17][CH2:18][CH2:19][CH3:20])[CH2:21][CH2:22][CH2:23][CH3:24])[CH:15]=[C:10]1[C:8]2=[O:9]

Participants

4

Reactant 2

HCID 5942759-Bromo-9-borabicyclo(3.3.1)nonaneHCID 67383097(5-Bromo-2-methoxyphenyl)(2,6-difluoro-5-(tributylstannyl)pyridin-3-yl)methanone

Product 1

HCID 673833207-bromo-2-fluoro-3-(tributylstannyl)-5H-chromeno[2,3-b]pyridin-5-one

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

(5-Bromo-2-methoxyphenyl)(2,6-difluoro-5-(tributylstannyl)pyridin-3-yl)methanone (6.48 g, 10.50 mmol) was dissolved in DCM (60 mL) under nitrogen and cooled in a dry ice bath to −78° C. 9-Bromo-9-borabicyclo[3.3.1]nonane, (1 M in DCM, 11.02 mL, 11.02 mmol) was added dropwise over 5 minutes and the reaction stirred for another 5 minutes. The flask was removed from the cold bath and stirred at ambient temperature for 20 minutes then saturated sodium bicarbonate (50 mL) was added to quench. Water (200 mL) and dichloromethane (100 mL) were added and the phases mixed and separated. The organic was dried with magnesium sulfate and evaporated to dryness under reduced pressure. Purification using silica chromatography (hexane to dichloromethane gradient) gave 7-bromo-2-fluoro-3-(tributylstannyl)-5H-chromeno[2,3-b]pyridin-5-one.

Workup

  1. customThe flask was removed from the cold bath
  2. stirringstirred at ambient temperature for 20 minutes
  3. additionsaturated sodium bicarbonate (50 mL) was added
  4. customto quench
  5. additionWater (200 mL) and dichloromethane (100 mL) were added
  6. additionthe phases mixed
  7. customseparated
  8. dry with materialThe organic was dried with magnesium sulfate
  9. customevaporated to dryness under reduced pressure
  10. customPurification

Sources & evidence

ORD record
ord-12fba29dc8274244b3098eb694eed3c6
Source dataset
uspto-grants-2014_11
Patent number
US08883782B2

Reaction notes

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