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

HRID 1919727ノート

反応式

HRID 1919727 の反応式
[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]

参加物

7

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 3

HCID 74505Methyltriphenyliphosphonium bromide触媒HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-30 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-69468e4eb4b94269bcfa441cb218047f
出典データセット
uspto-grants-2012_05
特許番号
US08168657B2

反応ノート

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