Triphenylphosphine → 1,1-dimethylethyl 3-(5-bromo-4-chloro-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-1-azetidinecarboxylate

HRID 1910014

Reaktionsgleichung

Reaktionsgleichung von HRID 1910014
[Br:1][C:2]1[C:10]2[C:5]([NH:6][CH:7]=[N:8][C:9]=2[Cl:11])=[N:4][CH:3]=1.O[CH:13]1[CH2:16][N:15]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:14]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCOC(/N=N/C(OCC)=O)=O>O1CCCC1>[Br:1][C:2]1[C:10]2[C:9]([Cl:11])=[N:8][CH:7]=[N:6][C:5]=2[N:4]([CH:13]2[CH2:14][N:15]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:16]2)[CH:3]=1

Komponenten

6

Edukt 4

HCID 11776TriphenylphosphineHCID 2756801Tert-butyl 3-hydroxyazetidine-1-carboxylateHCID 5462977Diethyl azodicarboxylateHCID 178478408HCID 178478408, Verbindung

Produkt 1

HCID 866636801,1-dimethylethyl 3-(5-bromo-4-chloro-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-1-azetidinecarboxylateAusbeute 80 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a solution of 5-bromo-4-chloro-1H-pyrrolo[2,3-d]pyrimidine (400 mg, 1.721 mmol), 1,1-dimethylethyl 3-hydroxy-1-azetidinecarboxylate (894 mg, 5.16 mmol) and triphenylphosphine (903 mg, 3.44 mmol) in Tetrahydrofuran (THF) (10 mL) was added dropwise DEAD (545 μl, 3.44 mmol). The solution was let stir at room temp. After 1 hr the reaction observed 10% product and the reaction was heated at 60° C. After 1 hr observed 80% desired product. Additional 100 mg of the 5-bromo-4-chloro-1H-pyrrolo[2,3-d]pyrimidine was added and heating was continued. The reaction was concentrated then loaded on to a 25 g SNAP column with 0 to 35% EtOAc in Hexane gradient over 30 minutes to give 1,1-dimethylethyl 3-(5-bromo-4-chloro-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-1-azetidinecarboxylate (624 mg, 94% yield) as a white solid. LC-MS (ES) m/z=386.9, 389.1 [M+H]+. 1H NMR (400 MHz, DMSO-d6) δ 8.69 (s, 1H), 8.38 (s, 1H), 5.53-5.62 (m, 1H), 4.33 (d, J=8.34 Hz, 4H), 1.43 (s, 9H).

Aufarbeitung

  1. temperaturethe reaction was heated at 60° C

Quellen und Nachweise

ORD-Eintrag
ord-d172328e522a44beaa90b321fa358b03
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08598156B2

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