Allyl Alcohol → 3-Allyl 1-tert-butyl 4-oxopyrrolidine-1,3-dicarboxylate

HRID 61353Notes

Reaction equation

HRID 61353 reaction equation
[O:1]=[C:2]1[CH2:6][N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH2:4][CH:3]1[C:14]([O:16][CH3:17])=[O:15].[CH2:18](O)[CH:19]=C.C([Sn](=O)CCCC)CCC>C1(C)C=CC=CC=1>[O:1]=[C:2]1[CH2:6][N:5]([C:7]([O:9][C:10]([CH3:11])([CH3:12])[CH3:13])=[O:8])[CH2:4][CH:3]1[C:14]([O:16][CH2:17][CH:18]=[CH2:19])=[O:15]

Participants

5

Reactant 3

HCID 7858Allyl Alcohol2×HCID 61221Dibutyltin oxideHCID 15815995Methyl 1-tert-butyloxycarbonyl-4-oxopyrrolidine-3-carboxylate

Product 1

HCID 675170133-Allyl 1-tert-butyl 4-oxopyrrolidine-1,3-dicarboxylateYield 90%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 1-tert-butyl 3-methyl 4-oxopyrrolidine-1,3-dicarboxylate (48.65 g, 0.20 mol), allyl alcohol (300 mL), and dibutyltin oxide (5.0 g, 20 mmol) in anhydrous toluene (800 mL) was refluxed for 20 h under a Dean-Stark trap with portionwise removal of solvent (total of 200 mL) over the first 6 hours, followed by addition of more allyl alcohol (75 mL) at the end of the first 6 hours. The reaction mixture was concentrated, dissolved in minimal methylene chloride, and loaded onto a silica gel column (700 mL volume) and eluted with methylene chloride, 10% then 15&, then 20% ethyl acetate/methylene chloride to afford 3-allyl 1-tert-butyl 4-oxopyrrolidine-1,3-dicarboxylate (48.6 g, 90%) as a pale pink oil (NMR and MS as above). This compound (48.47 g, 0.18 mol) was dissolved in anhydrous tetrahydrofuran (200 mL) and added to a stirred solution of Pd(PPh3)4 (4.16 g, 3.6 mmol) in anhydrous tetrahydrofuran (400 mL) under nitrogen, stirred for 4 h, and concentrated. The residue was dissolved in heptane and loaded onto a silica gel column (1000 mL volume) and eluted with 60:35:5 heptane/methylene chloride/ethyl acetate to afford tert-butyl 3-allyl-4-oxopyrrolidine-1-carboxylate (27.93, 69%) as a pale yellow oil (NMR and MS as above).

Workup

  1. concentrationThe reaction mixture was concentrated
  2. dissolutiondissolved in minimal methylene chloride
  3. washeluted with methylene chloride, 10%

Sources & evidence

ORD record
ord-f87455a32a7b4998b71eac6aed308a01
Source dataset
uspto-grants-2016_09
Patent number
US09440995B2

Reaction notes

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