2-Dicyclohexylphosphino-2',6'-dimethoxybiphenyl → 6-chloro-3-cyclobutyl-1-trityl-1H-pyrazolo[4,3-c]pyridine

HRID 571406Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 571406
[CH:1]1([Mg]Cl)[CH2:4][CH2:3][CH2:2]1.[Cl:7][C:8]1[N:13]=[CH:12][C:11]2[C:14](I)=[N:15][N:16]([C:17]([C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[C:10]=2[CH:9]=1.COC1C=CC=C(OC)C=1C1C=CC=CC=1P(C1CCCCC1)C1CCCCC1>[Cl-].[Zn+2].[Cl-].CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:7][C:8]1[N:13]=[CH:12][C:11]2[C:14]([CH:1]3[CH2:4][CH2:3][CH2:2]3)=[N:15][N:16]([C:17]([C:18]3[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=3)([C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=3)[C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)[C:10]=2[CH:9]=1

Komponenten

6

Edukt 3

HCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 895258586-Chloro-3-iodo-1-trityl-1H-pyrazolo[4,3-c]pyridineHCID 178478987HCID 178478987, Verbindung

Produkt 1

HCID 895258986-chloro-3-cyclobutyl-1-trityl-1H-pyrazolo[4,3-c]pyridineAusbeute 56 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 3007855ZincchlorideKatalysator

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

Reference: PCT Int. Appl., 2010056631, 2010. To a solution of zinc chloride (1.5 ml, 3.591 mmol, 1.9M in 2-methyl THF) at 0° C. was added a solution of cyclobutyl magnesium chloride in (9.20 ml, 4.60 mmol, 0.5 M in 2-methyl-THF). The reaction solution was stirred at 0° C. to r.t for 1 hr, and then transferred into a mixture of 6-chloro-3-iodo-1-trityl-1H-pyrazolo[4,3-c]pyridine (3a, 1 g, 1.917 mmol), Pd(OAc)2 (0.043 g, 0.192 mmol) and S-Phos (2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, 0.118 g, 0.287 mmol) at r.t. The result dark suspension was stirred at r.t for 3 hr and then was quenched with water and extracted with ethyl acetate. The organic layer was concentrated and purified by column chromatography on silica gel (50 g, eluting with 20% ethyl acetate/hexanes) to give 6-chloro-3-cyclobutyl-1-trityl-1H-pyrazolo[4,3-c]pyridine (483 mg, 56%) as a light yellow solid. MS ESI calc'd. for C29H24Cl1N3[M+1]+ 450, found 450.

Aufarbeitung

  1. stirringThe result dark suspension was stirred at r.t for 3 hr
  2. customwas quenched with water
  3. extractionextracted with ethyl acetate
  4. concentrationThe organic layer was concentrated
  5. custompurified by column chromatography on silica gel (50 g, eluting with 20% ethyl acetate/hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-45bc2396c79e4af3b0fecf125cbca8e4
Quelldatensatz
uspto-grants-2015_05
Patentnummer
US09023865B2

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