Tributylvinyltin → 6-Ethenylpyrido[2,3-b]pyrazine

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Reaktionsgleichung

Cl[C:2]1[CH:3]=[CH:4][C:5]2[C:6]([N:11]=1)=[N:7][CH:8]=[CH:9][N:10]=2.[CH:12]([Sn](CCCC)(CCCC)CCCC)=[CH2:13]>C1COCC1.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH:12]([C:2]1[CH:3]=[CH:4][C:5]2[C:6]([N:11]=1)=[N:7][CH:8]=[CH:9][N:10]=2)=[CH2:13]

Komponenten

Reaktionsbedingungen

Temperatur: 65 °C

Versuchsvorschrift

6-chloropyrido[2,3-b]pyrazine (Intermediate 4.2) (3 g, 18.12 mmol, 1.00 eq.) was dissolved in THF (150 mL) and degassed with nitrogen at rt for 10 minutes. Tetrakis (triphenylphosphine) palladium(0) (1.46 g, 1.27 mmol, 0.07 eq.) and vinyltributylstannane (7.47 mL, 23.5 mmol, 1.3 eq.) were added and reaction mixture was stirred at 65° C. for 3 hours. THF was evaporated and crude purified directly by flash chromatography using cyclohexane/ethyl acetate (8/2) to give 2.3 g of the expected compound (Intermediate 4.3) as an orange oil. Amount: 2.3 g; Yield: 81%; Formula: C9H7N3; HPLC Purity: 98%; HPLC H2O TFA 0.1%-ACN TFA 0.05%): Rt (min); Area %=1.32 min; 98%; 1H NMR (DMSO-d6) δ 9.10 (s, 1H), 8.98 (s, 1H), 8.46 (d, 1H, J=8 Hz), 7.95 (d, 1H, J=8 Hz), 6.90 (dd, 1H, Jtrans=17 Hz, Jcis=10 Hz), 6.50 (dd, 1H, Jtrans=17 Hz, Jgem=1.5 Hz), 5.80 (dd, 1H, Jcis=10 Hz, Jgem=1.5 Hz). LC-MS: M/Z ESI: Rt (min) 0.78 min, 158.13 (M+1).

Aufarbeitung

customdegassed with nitrogen at rt for 10 minutes
customreaction mixture
customTHF was evaporated
customcrude purified directly by flash chromatography

Quellen und Nachweise

ORD-Eintrag: ord-403f50eeb9d9475f9e8ceb10894fc18f
Quelldatensatz: uspto-grants-2010_11
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US07842698B2

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