Water → Ditert-butyl (2S,5S)-5-vinylpyrrolidine-1,2-dicarboxylate

HRID 594833Notes

Reaction equation

HRID 594833 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[K+].[C:11]([O:15][C:16]([N:18]1[C@H:22]([CH:23]=O)[CH2:21][CH2:20][C@H:19]1[C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])=[O:17])([CH3:14])([CH3:13])[CH3:12].[C@H:32](O)(C([O-])=O)[C@@H](O)C([O-])=O.[Na+].[K+].O>C1(C)C=CC=CC=1.C1COCC1>[C:11]([O:15][C:16]([N:18]1[C@H:22]([CH:23]=[CH2:32])[CH2:21][CH2:20][C@H:19]1[C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])=[O:17])([CH3:14])([CH3:13])[CH3:12]

Participants

7

Reactant 4

HCID 962WaterHCID 9357Potassium Sodium TartrateHCID 3251421Potassium bis(trimethylsilyl)amideHCID 131734565(S)-di-tert-butyl-5-formylpyrrolidine-1,2-dicarboxylate

Product 1

HCID 68171110Ditert-butyl (2S,5S)-5-vinylpyrrolidine-1,2-dicarboxylateYield 88%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

93.5 ml (61.69 mmol, 2.0 eq) of a solution of KHMDS in toluene (15 w %, ABCR) was added under argon at RT to a suspension of 22.037 g (61.69 mmol, 2.0 eq) Ph3PMeBr in 220 ml THF, and the substance was stirred for 1 h. Then, a solution of 9.234 g (30.88 mmol, 1.0 eq) of the aldehyde 111 in 70 ml THF was dropped in at −78° C., and the resulting solution was stirred for 2.5 h at RT. 160 ml saturated Rochelle salt solution and 100 ml water was added to the reaction mixture, then extracted 3× with 260 ml MTBE each, the combined organic phases were washed with saturated NaCl solution and dried over magnesium sulfate. The solvent was removed at reduced pressure and, after purification by means of column chromatography on silica gel with EtOAc/CyHex (1:9) as eluent, 8.091 g (27.21 mmol, 88%) of the vinyl proline 112 was obtained as an isomeric mixture (d.r.: 1.7:1 cis:trans).

Workup

  1. extractionextracted 3× with 260 ml MTBE each, the combined organic phases
  2. washwere washed with saturated NaCl solution
  3. dry with materialdried over magnesium sulfate
  4. customThe solvent was removed at reduced pressure
  5. customafter purification by means of column chromatography on silica gel with EtOAc/CyHex (1:9) as eluent

Sources & evidence

ORD record
ord-24f97eae61c74fa19714a15f56a4e18b
Source dataset
uspto-grants-2016_01
Patent number
US09242985B2

Reaction notes

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