tert-Butyl acrylate → tert-butyl (E)-3-[6-[N-(methoxycarbonylmethyl)amino]pyridin-3-yl]acrylate

HRID 1297383

Reaktionsgleichung

Reaktionsgleichung von HRID 1297383
Br[C:2]1[CH:3]=[CH:4][C:5]([NH:8][CH2:9][C:10]([O:12][CH3:13])=[O:11])=[N:6][CH:7]=1.[C:14]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])(=[O:17])[CH:15]=[CH2:16].CCN(C(C)C)C(C)C.CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>C(#N)CC.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:13][O:12][C:10]([CH2:9][NH:8][C:5]1[N:6]=[CH:7][C:2](/[CH:16]=[CH:15]/[C:14]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])=[CH:3][CH:4]=1)=[O:11]

Komponenten

7

Edukt 4

HCID 15458tert-Butyl acrylateHCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 22139049Methyl 2-((5-bromopyridin-2-yl)amino)acetate

Produkt 1

HCID 66905699tert-butyl (E)-3-[6-[N-(methoxycarbonylmethyl)amino]pyridin-3-yl]acrylateAusbeute 93,3 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 7854PropionitrileLösungsmittel

Versuchsvorschrift

A solution of 5-bromo-2-(methoxycarbonylmethyl)aminopyridine (4.69 g, 19.1 mmole, from Preparation 28 (c)), tert-butyl acrylate (11.2 mL, 76.5 mmole), DIEA (6.7 mL, 38.5 mmole), Pd(OAc)2 (215 mg, 1 mmole), and P(o-tol)3 (583 mg, 2 mmole) in propionitrile (100 mL) was purged with Ar, then was heated at reflux. After 18 h, the reaction was allowed to cool to room temperature then was concentrated to dryness. The residue was purified by flash chromatography on silica gel (40% EtOAc/hexane) to give the title compound (5.21 g, 93%) as a white solid: 1H NMR (400 MHz, CDCl3) δ 8.19 (s, 1H), 7.62 (dd, 1H), 7.47 (d, J=16.0 Hz, 1H), 6.48 (d, J=8.7 Hz, 1H), 6.17 (d, J=15.9 Hz, 1H), 5.21 (br s, 1H), 4.20 (d, J=5.4 Hz, 2H), 3.79 (s, 3H), 1.52 (s, 1H).

Aufarbeitung

  1. temperaturewas heated
  2. temperatureat reflux
  3. concentrationthen was concentrated to dryness
  4. customThe residue was purified by flash chromatography on silica gel (40% EtOAc/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-60fc89d70a204ff7b91c1aa6e04c662a
Quelldatensatz
uspto-grants-2007_07
Patentnummer
US07250424B2

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