Dichloromethane → 2-Hydroxy-5-[3-(2-methoxy-phenyl)-1-(toluene-sulfonyl)-1H-pyrrolo[2,3-b]pyridin-5-yl]-benzoic acid methyl ester

HRID 603023ノート

反応式

HRID 603023 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[C:9]1[C:17]2[C:12](=[N:13][CH:14]=[C:15](B3OC(C)(C)C(C)(C)O3)[CH:16]=2)[N:11]([S:27]([C:30]2[CH:35]=[CH:34][C:33]([CH3:36])=[CH:32][CH:31]=2)(=[O:29])=[O:28])[CH:10]=1.Br[C:38]1[CH:47]=[C:42]([C:43]([O:45][CH3:46])=[O:44])[C:41]([OH:48])=[CH:40][CH:39]=1.ClCCl>C([O-])(O)=O.[Na+].C(#N)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH3:46][O:45][C:43](=[O:44])[C:42]1[CH:47]=[C:38]([C:15]2[CH:16]=[C:17]3[C:9]([C:4]4[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=4[O:2][CH3:1])=[CH:10][N:11]([S:27]([C:30]4[C:31]([CH3:32])=[CH:36][CH:33]=[CH:34][CH:35]=4)(=[O:29])=[O:28])[C:12]3=[N:13][CH:14]=2)[CH:39]=[CH:40][C:41]=1[OH:48]

参加物

7

反応物 3

HCID 6344DichloromethaneHCID 77683Methyl 5-bromosalicylateHCID 160390673-(2-Methoxyphenyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1-tosyl-1H-pyrrolo[2,3-b]pyridine

生成物 1

HCID 670612012-Hydroxy-5-[3-(2-methoxy-phenyl)-1-(toluene-sulfonyl)-1H-pyrrolo[2,3-b]pyridin-5-yl]-benzoic acid methyl ester収率 91%

試薬・触媒・溶媒 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 6342Acetonitrile溶媒HCID 516892Sodium Bicarbonate溶媒

反応条件

温度
90 °C

実験手順

To a solution of 3-(2-methoxy-phenyl)-5-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1-(toluene-4-sulfonyl)-1H-pyrrolo[2,3-b]pyridine (502 mg, 1.00 mmol) in 1.5 mL saturated aqueous NaHCO3 and 5.0 mL acetonitrile was added methyl 5-bromosalicylate (253 mg, 1.10 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium (II), complex with dichloromethane (1.1) (41 mg, 0.05 mmol) in a microwave vial. The vial was capped, flushed with N2, evacuated under vacuum, and subsequently heated in a microwave at 90° C. for 300 seconds. The material was diluted with ethyl acetate and the organic layer was washed with saturated NaHCO3 (aq) and brine then dried over Na2SO4. The material was filtered, then adsorbed onto silica gel and purified by flash chromatography with a gradient of ethyl acetate and hexane, affording the title compound as a hydroscopic white solid (480 mg, 91% yield). 1H NMR (500 MHz, CD3OD) δ8.55 (d, J=2.0 Hz, 1H), 8.06 (m, 4H), 7.96 (s, 1H), 7.77 (dd. J=2.5, 6.0 Hz, 1H), 7.52 (dd, J=2.0, 6.0 Hz, 1H), 7.40 (m, 3H), 7.16 (d, J=8.5 Hz, 1H), 7.08 (m, 2H), 3.98 (s, 3H), 3.87 (s, 3H), 2.39 (s, 3H). MS: m/z 529.1 (M+H+).

後処理

  1. customThe vial was capped
  2. customflushed with N2
  3. customevacuated under vacuum
  4. additionThe material was diluted with ethyl acetate
  5. washthe organic layer was washed with saturated NaHCO3 (aq) and brine
  6. dry with materialthen dried over Na2SO4
  7. filtrationThe material was filtered
  8. custompurified by flash chromatography with a gradient of ethyl acetate and hexane

出典と根拠

ORDレコード
ord-a0326f505e434bfab4262bbe8ca67c7a
出典データセット
uspto-grants-2011_03
特許番号
US07906648B2

反応ノート

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