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

HRID 579521Notes

Reaction equation

HRID 579521 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].C[Si]([N-][Si](C)(C)C)(C)C.[Na+].Br[CH2:34][CH2:35][CH:36]=[CH2:37]>C1COCC1>[C:1]([O:5][C:6](=[O:22])[CH:7]([N:8]=[C:9]([C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1)[CH2:37][CH2:36][CH:35]=[CH2:34])([CH3:4])([CH3:2])[CH3:3]

Participants

5

Reactant 3

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

Product 1

HCID 160669741,1-Dimethylethyl 2-[(diphenylmethylene)amino]-5-hexenoateYield 94.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

While under a nitrogen atmosphere a stirred solution of (benzhydrylidene-amino)-acetic acid tert-butyl ester (5 g, 16.9 mmol) in THF (80 mL, 0.2 M) was carefully treated with sodium bis(trimethylsilyl)amide (18.6 mL, 1.0 M, 1.1 equiv) at −78° C. After stirring for 30 min, 4-bromo-but-1-ene (2.1 mL, 20.3 mmol, 1.2 equiv) was slowly added. The cooling bath was removed and the reaction mixture gradually warmed to room temperature and stirred for overnight. The solution was cooled to 0° C. and quenched with water. The resulting solution was diluted with ethyl acetate and washed successively with water and saturated aqueous NaCl, dried over MgSO4, filtered and concentrated. Purification by MPLC (1-25% ethyl acetate in heptane) gave 2-(benzhydrylidene-amino)-hex-5-enoic acid tert-butyl ester as colorless oil (5.6 g, 15.9 mmol, 94%).

Workup

  1. customThe cooling bath was removed
  2. stirringstirred for overnight
  3. temperatureThe solution was cooled to 0° C.
  4. customquenched with water
  5. additionThe resulting solution was diluted with ethyl acetate
  6. washwashed successively with water and saturated aqueous NaCl
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customPurification by MPLC (1-25% ethyl acetate in heptane)

Sources & evidence

ORD record
ord-1a24c120d9d042f78e7613297ca80e5d
Source dataset
uspto-grants-2015_05
Patent number
US09040703B2

Reaction notes

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