tert-Butyl 2-formylpiperidine-1-carboxylate → HCID 67498933, compound

HRID 1919717Notes

Reaction equation

HRID 1919717 reaction equation
[Li][CH2:2][CH2:3]CC.[C:6]([N:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH:14]1[CH:19]=O)([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)C.C1COCC1.O>[C:6]([N:13]1[CH2:18][CH2:17][CH2:16][CH2:15][CH:14]1/[CH:19]=[CH:2]\[CH3:3])([O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:7]

Participants

7

Reactant 3

HCID 10656219tert-Butyl 2-formylpiperidine-1-carboxylateHCID 21226206Ethyl acetate hexaneHCID 178418339Butyllithium

Product 1

HCID 67498933HCID 67498933, compoundYield 41%

Reagents, catalysts & solvents 3

HCID 73727Phosphonium, ethyltriphenyl-, bromide (1:1)CatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-30 °C

Procedure

A suspension of ethyltriphenylphosphonium bromide (7.31 g, 19.68 mmol) in 40 mL of THF was cooled to −30° C. and treated with n-BuLi (10.9 mL, 19.68 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 N-Boc-piperidine-2-carboxaldehyde (3.53 g, 17.89 mmol) in 10 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 1.6 g (41%) of the product which was homogenous by TLC analysis. 1H NMR (250 MHz) δ 5.73-5.51 (m, 2H), 5.05-5.01 (m, 1H), 3.98-3.93 (br d, 1H), 2.90-2.81 (m, 1H), 1.7-1.39 (m, 18H); 13C NMR (62.7 MHz) 154.8 (s), 128.0 (s), 125.8 (s), 79.0 (s), 47.7 (s), 39.6 (s), 30.3 (s), 28.5 (s), 25.6 (s), 19.5 (s), 13.2 (s) ppm.

Workup

  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

Sources & evidence

ORD record
ord-c473d4d0381b4870bf424eeed2b3ac61
Source dataset
uspto-grants-2012_05
Patent number
US08168657B2

Reaction notes

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