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

HRID 1919727노트

반응식

HRID 1919727 반응식
[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]

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 74505Methyltriphenyliphosphonium bromide촉매HCID 962Water용매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
-30 °C

실험 절차

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) δ 5.48-5.28 (m, 2H), 4.58-4.54 (m, 1H), 4.06-4.03 (m, 1H), 2.10-1.23 (m, 19H), 1.22-1.18 (d, 3H), 0.93-0.88 (t, 3H), 1H), 4.07-4.00 (m, 1H), 2.12-1.38 (m, 15H), 1.23-1.19 (d, 3H), 0.97-0.95 (t, 3H); 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.

후처리

  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

출처 및 근거

ORD 기록
ord-69468e4eb4b94269bcfa441cb218047f
출처 데이터셋
uspto-grants-2012_05
특허 번호
US08168657B2

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