Potassium bis(trimethylsilyl)amide → Boc-1(S)-cyclohexylmethylprop-2-en-1-ylamine

HRID 249396Notes

Reaction equation

HRID 249396 reaction equation
C[Si](C)(C)[N-][Si](C)(C)C.[K+].[I-].C1([C:18]([PH3+])([C:25]2[CH:30]=[CH:29]C=CC=2)[C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)C=CC=CC=1.[C:32]([N:39](C1CCCCC1)[C@H](C=O)C)([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33].C(N(C1CCCCC1)[C@H](CO)C)(OC(C)(C)C)=O>O1CCCC1.CS(C)=O>[C:35]([O:34][C:32]([NH:39][C@H:25]([CH:30]=[CH2:29])[CH2:18][CH:19]1[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24]1)=[O:33])([CH3:38])([CH3:37])[CH3:36]

Participants

7

Reactant 4

HCID 3251421Potassium bis(trimethylsilyl)amideHCID 18606792Boc cyclohexylalaninalHCID 66599960Tritylphosphanium iodideHCID 69175019Boc cyclohexylalaninol

Product 1

HCID 15601530Boc-1(S)-cyclohexylmethylprop-2-en-1-ylamineYield 60%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A 0° C. solution of potassium hexamethyldisilazide (22.9 mmol in 115 mL of 5:1, tetrahydrofuran (THF): dimethyl sulfoxide (DMSO) was added dropwise to triphenylmethylphosphonium iodide (24.81 mmol). After stirring at 0° C. for 1 hour, the solution was cooled to -78° C. and a solution of Boc-cyclohexylalaninal [4.90 g, 19.08 mmol, prepared by Swern oxidation (Mancuso, A. J.; Huang,, S. -L.; and Swern, D., J. Org. Chem. 1978, 43, 2480) of Boc cyclohexylalaninol] in dry THF (95 mL) was added. After stirring at -78° C. for 1 hour, the mixture was allowed to warm to room temperature. The reaction mixture was quenched with aqueous ammonium chloride and extracted with ether (2×300 mL). The combined organic phase was washed with 10% HCl (200 mL), saturated NaHSO3 (2×200 mL), H2O (2×200 mL), saturated NaHCO3 (2×200 mL), and brine (200 mL), dried (MgSO4), filtered, and evaporated. The residue was purified by chromatography (40 m SiO2 ; ether:hexane, 15:85) to give the desired compound in 60% yield. Mass spectrum: (M+H)+ =254.

Workup

  1. temperaturethe solution was cooled to -78° C.
  2. stirringAfter stirring at -78° C. for 1 hour
  3. temperatureto warm to room temperature
  4. customThe reaction mixture was quenched with aqueous ammonium chloride
  5. extractionextracted with ether (2×300 mL)
  6. washThe combined organic phase was washed with 10% HCl (200 mL), saturated NaHSO3 (2×200 mL), H2O (2×200 mL), saturated NaHCO3 (2×200 mL), and brine (200 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by chromatography (40 m SiO2 ; ether:hexane, 15:85)

Sources & evidence

ORD record
ord-7f07135d17614dfa8464657af384612f
Source dataset
uspto-grants-1993_05
Patent number
US05214129

Reaction notes

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