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

HRID 528963

反応式

HRID 528963 の反応式
[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]

参加物

9

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 24290Palladium Chloride触媒HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
70 °C

実験手順

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)+.

後処理

  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)

出典と根拠

ORDレコード
ord-b52b009c081e42fcbdc7882989b6f5a3
出典データセット
uspto-grants-2016_05
特許番号
US09346795B2

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