Dimethylformamide → tert-Butyl 4-formyl-3-(1,2,3,4-tetrahydroisoquinoline-2-carbonyl)benzoate

HRID 528963

반응식

HRID 528963 반응식
[C]=O.I[C:4]1[CH:16]=[CH:15][C:7]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])=[CH:6][C:5]=1[C:17]([N:19]1[CH2:28][CH2:27][C:26]2[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=2)[CH2:20]1)=[O:18].CCN(C(C)C)C(C)C.C([SiH](CCCCCCCC)CCCCCCCC)CCCCCCC.CN([CH:66]=[O:67])C>CCOC(C)=O.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].[Pd](Cl)Cl>[CH:66]([C:4]1[CH:16]=[CH:15][C:7]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])=[CH:6][C:5]=1[C:17]([N:19]1[CH2:28][CH2:27][C:26]2[C:21](=[CH:22][CH:23]=[CH:24][CH:25]=2)[CH2:20]1)=[O:18])=[O:67]

참가 물질

9

반응물 5

HCID 6228DimethylformamideHCID 81531DiisopropylethylamineHCID 87780Trioctylsilane, 95%HCID 71062274tert-Butyl 4-iodo-3-(1,2,3,4-tetrahydroisoquinoline-2-carbonyl)benzoateHCID 178418416HCID 178418416, 화합물

생성물 1

HCID 86718914tert-Butyl 4-formyl-3-(1,2,3,4-tetrahydroisoquinoline-2-carbonyl)benzoate수율 50%

시약·촉매·용매 3

HCID 24290Palladium Chloride촉매HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)촉매HCID 8857Ethyl Acetate용매

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온도
70 °C

실험 절차

Carbon monoxide was bubbled through a solution of tert-butyl 4-iodo-3-(1,2,3,4-tetrahydroisoquinoline-2-carbonyl)benzoate (1.36 g, 2.94 mmol) and 1,1′-bis-(diphenylphosphino)-ferrocene) palladium dichloride (0.241 g, 0.294 mmol) in DMF (20 mL) at 70° C. for 10 min. DIPEA (1.28 mL, 7.34 mmol) and trioctylsilane (2.64 mL, 5.87 mmol) were added. The reaction mixture was stirred at 70° C. under CO (balloon) overnight. After cooling to room temperature, the reaction mixture was diluted with EtOAc and washed with sat. aq. sodium bicarbonate solution, 10% aq. LiCl solution, and then sat. aq. sodium bicarbonate solution again. The organic layer was dried over anhydrous sodium sulfate and concentrated in vacuo. The residue was purified by flash chromatography (Isco 40 g column eluting from 0-40% EtOAc/hexanes) to give the title compound (537 mg, 50%) as a yellow foam. 1H NMR (CDCl3, 1.5:1 mixture of amide rotamers) δ 10.19 (s, 0.5H), 10.14 (s, 0.5H), 8.17-8.13 (m, 1H), 8.03-7.98 (m, 2H), 7.26-7.10 (m, 4H), 5.00 (s, 1H), 4.33 (m, 1H), 4.09 (t, J=6 Hz, 1H), 3.45 (t, J=6 Hz, 1H), 3.04 (t, J=6 Hz, 1H), 2.80 (t, J=6 Hz, 1H), 1.61 (s, 9H); MS(ESI+) m/z 366.2 (M+H)+.

후처리

  1. temperatureAfter cooling to room temperature
  2. washwashed with sat. aq. sodium bicarbonate solution, 10% aq. LiCl solution
  3. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by flash chromatography (Isco 40 g column eluting from 0-40% EtOAc/hexanes)

출처 및 근거

ORD 기록
ord-b52b009c081e42fcbdc7882989b6f5a3
출처 데이터셋
uspto-grants-2016_05
특허 번호
US09346795B2

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