Triphenylphosphine → (R)-di-tert-butyl 1-((tetrahydrofuran-2-yl)methyl)hydrazine-1,2-dicarboxylate

HRID 1921299Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1921299
[O:1]1[CH2:5][CH2:4][CH2:3][C@@H:2]1[CH2:6]O.[NH:8]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[NH:9][C:10]([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(/C(OC(C)(C)C)=O)=N\C(OC(C)(C)C)=O>C1COCC1.O>[O:1]1[CH2:5][CH2:4][CH2:3][C@@H:2]1[CH2:6][N:8]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[NH:9][C:10]([O:12][C:13]([CH3:14])([CH3:15])[CH3:16])=[O:11]

Komponenten

7

Edukt 4

HCID 11776TriphenylphosphineHCID 85431Di-tert-butyl bicarbamateHCID 6034084Di-tert-butyl diazene-1,2-dicarboxylateHCID 6931745(2R)-oxolan-2-ylmethanol

Produkt 1

HCID 66643239(R)-di-tert-butyl 1-((tetrahydrofuran-2-yl)methyl)hydrazine-1,2-dicarboxylateAusbeute 205,7 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To (R)-(tetrahydrofuran-2-yl)methanol (4.0 g, 39.2 mmol), di-tert-butyl hydrazine-1,2-dicarboxylate (3.64 g, 15.67 mmol) and triphenylphosphine (15.41 g, 58.7 mmol) in THF (100 mL) was added (E)-di-tert-butyl diazene-1,2-dicarboxylate (13.5 g, 5.87 mmol). The mixture was stirred at ambient temperature for 3 h then diluted with water and extracted with EtOAc (100 mL×2). The organic extract was washed with brine and concentrated. Purification by flash chromatography (silica gel, 5-30% EtOAc/hexane) afforded 10.2 g (82%) of (R)-di-tert-butyl 1-((tetrahydrofuran-2-yl)-methyl)-hydrazine-1,2-dicarboxylate, which was dissolved in a solution of 4M HCl in dioxane (40 mL) and stirred at ambient temperature overnight. The solvent was removed under reduced pressure and ethyl acetate (20 mL) was added with stirring. The solid precipitate was filtered, washed with ether (10 mL) and dried in vacuum to yield 7.8 g (97%) of the title compound as a white solid. 1H NMR (300 MHz, DMSO-d6) δ ppm 1.48-1.63 (m, 1H), 1.73-1.88 (m, 2H), 1.90-2.02 (m, 1H), 2.84-3.01 (m, 2H), 3.61-3.71 (m, 1H), 3.72-3.83 (m, 1H), 3.97-4.08 (m, 1H), 5.76 (br, 5H); MS (ESI) m/z 117 (M+H)+.

Aufarbeitung

  1. extractionextracted with EtOAc (100 mL×2)
  2. extractionThe organic extract
  3. washwas washed with brine
  4. concentrationconcentrated
  5. customPurification by flash chromatography (silica gel, 5-30% EtOAc/hexane)

Quellen und Nachweise

ORD-Eintrag
ord-457082cf448c49389756ccf9f3bc7c1f
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08173687B2

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