N,N,N',N'-Tetramethylethylenediamine → HCID 66977049, compound

HRID 712234Notes

Reaction equation

HRID 712234 reaction equation
[Li+].[CH3:2][Si]([N-][Si](C)(C)C)(C)C.[N:11]1([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:16][CH2:15][CH:14]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:13][CH2:12]1.CN([CH2:32][CH2:33]N(C)C)C>C1COCC1.[CH2-]C=C.[CH2-]C=C.Cl[Pd+].Cl[Pd+]>[CH:33]1([C:14]2([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:13][CH2:12][N:11]([C:22]([O:24][C:25]([CH3:27])([CH3:26])[CH3:28])=[O:23])[CH2:16][CH2:15]2)[CH2:32][CH2:2]1

Participants

6

Reactant 3

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 2733832Lithium HexamethyldisilazideHCID 27588121-Tert-butyl 4-ethyl piperidine-1,4-dicarboxylate

Product 1

HCID 66977049HCID 66977049, compoundYield 28%

Reagents, catalysts & solvents 2

HCID 61538Palladium, di-mu-chlorobis(eta3-2-propenyl)di-CatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

LHMDS (1M THF solution; 2.4 mL, 2.4 mmol) was added to a −78° C. solution of 1-tert-butyl 4-ethyl piperidine-1,4-dicarboxylate (514 mg, 2 mmol) in anhydrous THF (5 mL) and the reaction was allowed to warm to 0° C. over the course of 30 mins, whilst under an inert atmosphere. This solution was added drop-wise to a solution of allylpalladium chloride dimer (365 mg, 1 mmol), TMEDA (302 uL, 2 mmol) in anhyrdous THF (2.5 mL) in an oven dried flask under an inert atmosphere at −60° C. A balloon of carbon monoxide was attached and the reaction stirred for 2.5 h at 0° C. Saturated ammonium chloride solution (10 mL) was added, the reaction mixture extracted with Et2O (20 mL) and the organic phase washed with sat. brine (20 mL), dried (MgSO4) and concentrated in vacuo. The desired product was isolated as an oil by normal phase chromatography (Grace 12 g, 25-75% hexane:EtOAc, gradient elution; visualised with permangenate stain) (164 mg, 28% yield). 1H NMR (CDCl3) δ 4.16 (q, J=7.1 Hz, 2H), 4.08-3.84 (m, 2H), 2.72 (s, 2H), 1.99 (dd, J=13.5, 2.0 Hz, 2H), 1.43 (s, 9H), 1.33-1.16 (m, 5H), 0.91 (tt, J=8.1, 5.8 Hz, 1H), 0.41-0.26 (m, 4H).

Workup

  1. customdried flask under an inert atmosphere at −60° C
  2. additionSaturated ammonium chloride solution (10 mL) was added
  3. extractionthe reaction mixture extracted with Et2O (20 mL)
  4. washthe organic phase washed with sat. brine (20 mL)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e7f2632f7a1c49708ac8c6ad37f637f6
Source dataset
uspto-grants-2015_11
Patent number
US09181234B2

Reaction notes

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