Triphenylphosphine → 1,2-Dibenzyl 3-(tert-butyl) (2S,3S)-5-methylenepiperidine-1,2,3-tricarboxylate

HRID 473761Notes

Reaction equation

HRID 473761 reaction equation
O=[C:2]1[CH2:7][N:6]([C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:9])[C@H:5]([C:18]([O:20][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[O:19])[C@@H:4]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])[CH2:3]1.[CH:35]1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>C1(C)C=CC=CC=1.C1(C)C=CC=CC=1.C1COCC1.C(OCC)(=O)C>[CH2:35]=[C:2]1[CH2:7][N:6]([C:8]([O:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[O:9])[C@H:5]([C:18]([O:20][CH2:21][C:22]2[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=2)=[O:19])[C@@H:4]([C:28]([O:30][C:31]([CH3:33])([CH3:34])[CH3:32])=[O:29])[CH2:3]1

Participants

6

Reactant 2

HCID 11776TriphenylphosphineHCID 593051041,2-Dibenzyl 3-(tert-butyl) (2S,3S)-5-oxopiperidine-1,2,3-tricarboxylate

Product 1

HCID 161089371,2-Dibenzyl 3-(tert-butyl) (2S,3S)-5-methylenepiperidine-1,2,3-tricarboxylate

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolventHCID 22635083Tetrahydrofuran tolueneSolvent

Procedure

To a solution of 1,2-dibenzyl 3-tert-butyl (2S,3S)-5-oxopiperidine-1,2,3-tricarboxylate of step 1n (850 mg) in toluene (10 mL) was added dropwise a solution of Ph3P═CH2 (0.25M in toluene/THF (3:1), 9.1 mL) at −10° C. The mixture was stirred and allowed to warm to RT during a period of 2 h. The mixture was diluted with ethyl acetate (75 mL) and washed with brine (3×25 mL). The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The residue was flash chromatographed on silica gel column to afford 1,2-dibenzyl 3-tert-butyl (2S,3S)-5-methylenepiperidine-1,2,3-tricarboxylate (546 mg). MS (ESI): 488.1 (M+Na+); 366.1 (M+H+—COO(t-Bu)).

Workup

  1. washwashed with brine (3×25 mL)
  2. dry with materialThe organic layer was dried over Na2SO4
  3. concentrationconcentrated under reduced pressure
  4. customchromatographed on silica gel column

Sources & evidence

ORD record
ord-40925c39b52f4ac894f529406006327b
Source dataset
uspto-grants-2014_01
Patent number
US08637497B2

Reaction notes

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