Tetrahydrofuran → 1,1-Dimethylethyl 2-[(diphenylmethylene)amino]-5-hexenoate

HRID 579545

Reaction equation

HRID 579545 reaction equation
[C:1]([O:5][C:6](=[O:22])[CH2:7][N:8]=[C:9]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)([CH3:4])([CH3:3])[CH3:2].Br[CH2:24][CH2:25][CH:26]=[CH2:27].C1COCC1.C[Si]([N-][Si](C)(C)C)(C)C.[Na+]>C(OCC)C>[C:16]1([C:9](=[N:8][CH:7]([CH2:27][CH2:26][CH:25]=[CH2:24])[C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:22])[C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=2)[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 21241Homoallyl bromideHCID 688171N-(Diphenylmethylene)glycine tert-butyl esterHCID 2724254Sodium bis(trimethylsilyl)amide

Product 1

HCID 160669741,1-Dimethylethyl 2-[(diphenylmethylene)amino]-5-hexenoateYield 94%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

While under an atmosphere of argon, a solution of N-(diphenylmethylene)glycine tert-butyl ester (6.30 g, 21.33 mmol) and 4-bromo-butene (3.45 g, 25.56 mmol) in freshly distilled THF (50 mL) was cooled to −78° C. and treated with sodium bis(trimethylsilyl)amide (23.4 mL, 1.0 M in THF). Once the addition was complete, the reaction was warmed to room temperature and stirred for 16 h, cooled to 0° C., diluted with ethyl ether and washed successively with saturated aqueous NaHCO3 and saturated aqueous NaCl, dried over MgSO4, filtered and concentrated. Rapid purification by MPLC (1-25% ethyl acetate in heptane over 8 CV) gave product tert-butyl 2-(diphenylmethyleneamino)hex-5-enoate as a colorless oil (7.00 g, 94%). Rf 0.50 (30% ethyl acetate in heptane).

Workup

  1. additionOnce the addition
  2. temperaturecooled to 0° C.
  3. washwashed successively with saturated aqueous NaHCO3 and saturated aqueous NaCl
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customRapid purification by MPLC (1-25% ethyl acetate in heptane over 8 CV)

Sources & evidence

ORD record
ord-3f97ef19311e49cc876029c1e88f0688
Source dataset
uspto-grants-2015_05
Patent number
US09040703B2

Linked notes

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