Dichloromethane → methyl 4-[2-(4'-nitro-1,1'-biphenyl-4-yl)-2-oxoethyl]tetrahydro-2H-pyran-4-carboxylate

HRID 9536

반응식

HRID 9536 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:20])[CH2:9][C:10]2([C:16]([O:18][CH3:19])=[O:17])[CH2:15][CH2:14][O:13][CH2:12][CH2:11]2)=[CH:4][CH:3]=1.[N+:21]([C:24]1[CH:29]=[CH:28][C:27](B(O)O)=[CH:26][CH:25]=1)([O-:23])=[O:22].C(=O)([O-])[O-].[Na+].[Na+].ClCCl>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].O.O1CCOCC1.C1(C)C=CC=CC=1>[N+:21]([C:24]1[CH:29]=[CH:28][C:27]([C:2]2[CH:7]=[CH:6][C:5]([C:8](=[O:20])[CH2:9][C:10]3([C:16]([O:18][CH3:19])=[O:17])[CH2:15][CH2:14][O:13][CH2:12][CH2:11]3)=[CH:4][CH:3]=2)=[CH:26][CH:25]=1)([O-:23])=[O:22]

참가 물질

9

반응물 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 27735524-Nitrophenylboronic acidHCID 21985831Methyl 4-[2-(4-bromophenyl)-2-oxoethyl]tetrahydro-2H-pyran-4-carboxylate

생성물 1

HCID 21985756methyl 4-[2-(4'-nitro-1,1'-biphenyl-4-yl)-2-oxoethyl]tetrahydro-2H-pyran-4-carboxylate수율 79.3%

시약·촉매·용매 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 962Water용매HCID 1140Toluene용매HCID 312751,4-Dioxane용매

반응 조건

온도
85 °C

실험 절차

Methyl 4-[2-(4-bromophenyl)-2-oxoethyl]tetrahydro-2H-pyran-4-carboxylate (820 mg, 2.40 mmol) and 4-nitrophenyl boronic acid (481 mg, 2.88 mmol) were combined in a dry flask under argon. Toluene (20 mL) and dioxane (5 mL) were added, and the resulting solution was degassed for 30 minutes by a flow of argon. The degassing was continued during the addition of saturated aqueous sodium carbonate (6 mL) and [1,1′-bis(diphenylphosphino)-ferrocene]dichloro palladium(II), 1:1 complex with dichloromethane (98 mg, 0.12 mmol). The resulting mixture was then heated at 85° C. for 16 h before it was cooled to rt. Water was added, and the aqueous layer was extracted twice with ethyl acetate. The combined organic phases were then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was purified by flash chromatography (Biotage Flash 40) using 1:1 ethyl acetate/hexane to afford methyl 4-[2-(4′-nitro-1,1′-biphenyl-4-yl)-2-oxoethyl]tetrahydro-2H-pyran-4-carboxylate (730 mg, 79%). LC-MS ret. time 3.03; m/z 383.9 (MH+); 1H NMR (300 MHz, CDCl3) δ 1.65–1.73 (m, 2H), 2.17–2.21 (m, 2H), 3.37 (s, 2H), 3.68 (s, 3H), 3.71–3.78 (m, 4H), 7.70 (d, 2H), 7.77 (d, 2H), 8.02 (d, 2H), 8.31 (d, 2H).

후처리

  1. customthe resulting solution was degassed for 30 minutes by a flow of argon
  2. temperaturewas cooled to rt
  3. extractionthe aqueous layer was extracted twice with ethyl acetate
  4. dry with materialThe combined organic phases were then dried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe resulting residue was purified by flash chromatography (Biotage Flash 40)

출처 및 근거

ORD 기록
ord-95ac54c9a77a48bb970bfef33b2bcba5
출처 데이터셋
uspto-grants-2006_08
특허 번호
US07091228B2

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