Methyl 2-((tert-butoxycarbonyl)amino)pent-4-ynoate → HCID 59750578、化合物

HRID 910724ノート

反応式

HRID 910724 の反応式
[CH2:1]([O:8][C:9](=[O:22])[NH:10][CH2:11][CH2:12][C:13]#[C:14][C:15]1[CH:20]=[CH:19][C:18](I)=[CH:17][CH:16]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:23][O:24][C:25](=[O:38])[C@H:26]([NH:30][C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:27][C:28]#[CH:29].COC(=O)C(NC(OC(C)(C)C)=O)CC#C>C1COCC1.C(N(CC)CC)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:23][O:24][C:25](=[O:38])[C@H:26]([NH:30][C:31]([O:33][C:34]([CH3:36])([CH3:35])[CH3:37])=[O:32])[CH2:27][C:28]#[C:29][C:18]1[CH:19]=[CH:20][C:15]([C:14]#[C:13][CH2:12][CH2:11][NH:10][C:9]([O:8][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[O:22])=[CH:16][CH:17]=1

参加物

8

反応物 3

HCID 10537281Methyl 2-((tert-butoxycarbonyl)amino)pent-4-ynoateHCID 12149490(R)-2-(Boc-amino)-4-pentynoic acid methyl esterHCID 59750570Benzyl [4-(4-iodophenyl)but-3-yn-1-yl]carbamate2 回

生成物 1

HCID 59750578HCID 59750578、化合物収率 99%

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 178418476HCID 178418476、化合物触媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8471Triethylamine溶媒

実験手順

Compound 22, [4-(4-iodophenyl)-but-3-ynyl]carbamic acid benzyl ester (0.52 g, 1.283 mmol) was dissolved in a mixture of anhydrous THF and triethylamine (8 mL, 1/1, v/v). To the solution was added copper (I) iodide (0.025 g, 0.128 mmol). The mixture was stirred at room temperature for 15 min. The flask was then evacuated and re-filled with Argon. The procedure was repeated three more times to ensure no oxygen remained. The catalyst, dichlorobis(triphenylphosphine)palladium(II) (0.09 g, 0.128 mmol) was added into the mixture under Argon protection. The mixture was further stirred at room temperature for 30 min. The other starting material 23, 2-tert-butoxycarbonylamino-pent-4-ynoic acid methyl ester (0.32 g, 1.412 mmol), dissolved in THF (4 mL) was added dropwise over 15 min. The newly formed reaction mixture was further stirred overnight at room temperature. The solid in the reaction mixture was vacuum filtered. The filtrate was concentrated. The residue was re-dissolved in dichloromethane and purified by column chromatography, eluting with a mixture of ethyl acetate (0-25%) and hexanes (100-75%) to afford the product 24 (0.64 g, 99%) as a gummy, yellowish solid. 1H NMR (300 MHz, CDCl3): δ 1.46 (s, 9H), 2.64 (t, J=6.3 Hz, 2H), 2.95 (t, J=4.1 Hz, 2H), 3.42 (m, 2H), 3.79 (s, 3H), 4.56 (m, 1H), 5.12 (s, 2H), 5.38 (br s, 1H), 7.29 (s, 4H), 7.35 (m, 5H). m/z (APCI) 502 [C29H32N2O6—H]+.

後処理

  1. customThe flask was then evacuated
  2. additionre-filled with Argon
  3. stirringThe mixture was further stirred at room temperature for 30 min
  4. additionwas added dropwise over 15 min
  5. customThe newly formed reaction mixture
  6. stirringwas further stirred overnight at room temperature
  7. filtrationfiltered
  8. concentrationThe filtrate was concentrated
  9. dissolutionThe residue was re-dissolved in dichloromethane
  10. custompurified by column chromatography
  11. washeluting with a mixture of ethyl acetate (0-25%) and hexanes (100-75%)

出典と根拠

ORDレコード
ord-55b933a5f1d24d679a8e40dd1be1c260
出典データセット
uspto-grants-2011_09
特許番号
US08022210B2

反応ノート

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