tert-butyl (2R,6S)-2-formyl-6-methylpiperidine-1-carboxylate → trans-N-Boc-2-(1-pentenyl)-6-methylpiperidine

HRID 840691Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 840691
[Li][CH2:2][CH2:3][CH2:4][CH3:5].[C:6]([N:13]1[C@@H:18]([CH:19]=O)[CH2:17][CH2:16][CH2:15][C@@H:14]1[CH3:21])([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7].CCOC(C)=O.CCCCCC>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.C1COCC1.O>[C:6]([N:13]1[C@@H:14]([CH3:21])[CH2:15][CH2:16][CH2:17][C@@H:18]1[CH:19]=[CH:2][CH2:3][CH2:4][CH3:5])([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7]

Komponenten

7

Edukt 3

HCID 10878893tert-butyl (2R,6S)-2-formyl-6-methylpiperidine-1-carboxylateHCID 21226206Ethyl acetate hexaneHCID 178418339Butyllithium

Produkt 1

HCID 67498452trans-N-Boc-2-(1-pentenyl)-6-methylpiperidineAusbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 74505Methyltriphenyliphosphonium bromideKatalysatorHCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
-30 °C

Versuchsvorschrift

A suspension of methyltriphenylphosphonium bromide (5.29 g, 13.25 mmol) in 27 mL of THF was cooled to −30° C. and treated with n-BuLi (6.13 mL, 13.44 mmol) dropwise. The deep red solution was slowly warmed to 0° C., stirred for 30 min, and then cooled to −78° C. The ylide was treated with a solution of trans-N-Boc-2-Methyl-6-Piperidinecarboxaldehyde (2.00 g, 9.46 mmol) in 3 mL of THF, and the mixture was slowly warmed to room temperature. The mixture was diluted with water, and the organic layer was separated. The aqueous layer was extracted with ether and the combined extracts were dried over K2CO3 and then concentrated to give a crude product as an oil. Chromatography on silica with 5% EtOAc/hexane afforded 2.53 g (87%) of the product which was homogeneous by TLC analysis. 1H NMR (250 MHz) δ5.48-5.28 (m, 2 H), 4.58-4.54 (m, 1 H), 4.06-4.03 (m, 1 H), 2.10-1.23 (m, 19 H), 1.22-1.18 (d, 3 H), 0.93-0.88 (t, 3 H); , 1 H), 4.07-4.00 (m, 1 H), 2.12-1.38 (m, 15 H), 1.23-1.19 (d, 3 H), 0.97-0.95 (t, 3 H); 13C NMR (62.7 MHz) 155.5 (s), 132.4 (s), 129.2 (s), 78.9 (s), 49.1 (s), 47.5 (s), 29.4 (s), 28.5 (s), 28.2 (s), 27.8 (s), 22.8 (s), 20.2 (s), 15.0 (s), 13.9 (s) ppm.

Aufarbeitung

  1. temperatureThe deep red solution was slowly warmed to 0° C.
  2. temperaturecooled to −78° C
  3. temperaturethe mixture was slowly warmed to room temperature
  4. customthe organic layer was separated
  5. extractionThe aqueous layer was extracted with ether
  6. dry with materialthe combined extracts were dried over K2CO3
  7. concentrationconcentrated
  8. customto give a crude product as an oil

Quellen und Nachweise

ORD-Eintrag
ord-e712d659e0e3451eb13eaea3d45318ec
Quelldatensatz
uspto-grants-2002_04
Patentnummer
US06369078B1

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