Dichloromethane → (S)-2-tert-butoxy-2-(7-(4-chlorophenyl)-5-methyl-2-(1-methyl-1H-pyrazolo[4,3-b]pyridine-6-yl)benzo[d]thiazol-6-yl)ethyl pivalate

HRID 510284ノート

反応式

HRID 510284 の反応式
Br[C:2]1[CH:3]=[C:4]2[N:10]([CH3:11])[N:9]=[CH:8][C:5]2=[N:6][CH:7]=1.B1(B2OC(C)(C)C(C)(C)O2)OC(C)(C)C(C)(C)O1.ClCCl.C([O-])(=O)C.[K+].[C:38]([O:44][CH2:45][C@H:46]([C:52]1[C:61]([CH3:62])=[CH:60][C:55]2[N:56]=[C:57](Br)[S:58][C:54]=2[C:53]=1[C:63]1[CH:68]=[CH:67][C:66]([Cl:69])=[CH:65][CH:64]=1)[O:47][C:48]([CH3:51])([CH3:50])[CH3:49])(=[O:43])[C:39]([CH3:42])([CH3:41])[CH3:40].C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.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.O>[C:38]([O:44][CH2:45][C@@H:46]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])[C:52]1[C:61]([CH3:62])=[CH:60][C:55]2[N:56]=[C:57]([C:2]3[CH:3]=[C:4]4[N:10]([CH3:11])[N:9]=[CH:8][C:5]4=[N:6][CH:7]=3)[S:58][C:54]=2[C:53]=1[C:63]1[CH:64]=[CH:65][C:66]([Cl:69])=[CH:67][CH:68]=1)(=[O:43])[C:39]([CH3:41])([CH3:40])[CH3:42]

参加物

10

反応物 6

HCID 6344DichloromethaneHCID 11430Potassium CarbonateHCID 517044Potassium AcetateHCID 2733548Bis(pinacolato)diboraneHCID 401522616-Bromo-1-methyl-1H-pyrazolo(4,3-b)pyridineHCID 86699799(S)-2-(2-bromo-7-(4-chlorophenyl)-5-methylbenzo[d]thiazol-6-yl)-2-tert-butoxyethyl pivalate

生成物 1

HCID 86699816(S)-2-tert-butoxy-2-(7-(4-chlorophenyl)-5-methyl-2-(1-methyl-1H-pyrazolo[4,3-b]pyridine-6-yl)benzo[d]thiazol-6-yl)ethyl pivalate

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

To a solution of 6-bromo-1-methyl-1H-pyrazolo[4,3-b]pyridine (20 mg, 0.094 mmol) in dioxane (2 mL) was added bis(pinacolato)diboron (29 mg, 0.113 mmol), [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane (8 mg, 0.0094 mmol), potassium acetate (19 mg, 0.189 mmol). The mixture was degassed and heated at 100° C. for 2 h. The mixture was cooled, and then added (S)-2-(2-bromo-7-(4-chlorophenyl)-5-methylbenzo[d]thiazol-6-yl)-2-tert-butoxyethyl pivalate (25 mg, 0.046 mmol), tetrakis(triphenylphosphine)palladium(0) (6 mg, 0.005 mmol), K2CO3 (33 mg, 0.23 mmol) and water (0.3 mL, degassed). The reaction mixture was heated at 90° C. for 1 h, cooled and partitioned between ethyl acetate and brine. The organic layer was separated, dried over Na2SO4, filtered and concentrated to give crude product which was purified by chromatographic column to afford the desired product. LCMS-ESI+: calc'd for C32H35ClN4O3S: 591.22 (M+H+); Found: 591.2 (M+H+).

後処理

  1. customThe mixture was degassed
  2. temperatureThe mixture was cooled
  3. temperatureThe reaction mixture was heated at 90° C. for 1 h
  4. temperaturecooled
  5. custompartitioned between ethyl acetate and brine
  6. customThe organic layer was separated
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give crude product which
  11. customwas purified by chromatographic column

出典と根拠

ORDレコード
ord-d43811f7bdad454e915a881b400e9b90
出典データセット
uspto-grants-2015_08
特許番号
US09096586B2

反応ノート

読み込み中…