Benzyl prop-2-yn-1-ylcarbamate → Benzyl 3-(6-{3-[(tert-butoxycarbonyl)amino]prop-1-ynyl}pyridin-3-yl)prop-2-ynylcarbamate

HRID 49568ノート

反応式

HRID 49568 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]([C:8]#[C:9][CH2:10][NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[N:6][CH:7]=1.[C:19]([NH:29][CH2:30][C:31]#[CH:32])([O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:20]>C(NC(C)C)(C)C.C(OCC)(=O)C.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.[Cu]I>[C:14]([O:13][C:12]([NH:11][CH2:10][C:9]#[C:8][C:5]1[N:6]=[CH:7][C:2]([C:32]#[C:31][CH2:30][NH:29][C:19](=[O:20])[O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[CH:3][CH:4]=1)=[O:18])([CH3:17])([CH3:16])[CH3:15]

参加物

7

反応物 2

HCID 11137906Benzyl prop-2-yn-1-ylcarbamateHCID 21299384tert-Butyl 3-(5-bromopyridin-2-yl)prop-2-ynylcarbamate

生成物 1

HCID 21299383Benzyl 3-(6-{3-[(tert-butoxycarbonyl)amino]prop-1-ynyl}pyridin-3-yl)prop-2-ynylcarbamate収率 55.1%

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 7912Diisopropylamine溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A mixture of tert-butyl 3-(5-bromopyridin-2-yl)prop-2-ynylcarbamate (3-1) (1.44 g), N-Cbz propargylamine (1.09 g), Pd(PPh3)2Cl2 (73 mg), and CuI (10 mg) in diisopropylamine (25 mL) was heated under reflux under a nitrogen atmosphere for 3 hours. The mixture was cooled to ambient temperature and diluted with ethyl acetate (70 mL). The precipitates were filtered and rinsed with ethyl acetate (30 mL). The filtrate and washings were combined, concentrated under reduced pressure, and purified by silica gel column chromatography using a mixture of MTBE and hexanes (2:3 to 4:1). The fractions containing the product were combined and concentrated under reduced pressure. The residue was crystallized from MTBE. Crystals were filtered, washed with MTBE, and dried to give 6-1 (1.07 g). An additional 120 mg of 6-1 was isolated from the mother liquors and washings.

後処理

  1. temperaturewas heated
  2. temperatureunder reflux under a nitrogen atmosphere for 3 hours
  3. filtrationThe precipitates were filtered
  4. washrinsed with ethyl acetate (30 mL)
  5. concentrationconcentrated under reduced pressure
  6. custompurified by silica gel column chromatography
  7. additiona mixture of MTBE and hexanes (2:3 to 4:1)
  8. additionThe fractions containing the product
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was crystallized from MTBE
  11. filtrationCrystals were filtered
  12. washwashed with MTBE
  13. customdried

出典と根拠

ORDレコード
ord-8736816034304086904f1b92f0cec74b
出典データセット
uspto-grants-2004_03
特許番号
US06706885B2

反応ノート

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