HCID 86650159, compound → HCID 86650158, compound

HRID 1808702Notes

Reaction equation

HRID 1808702 reaction equation
[C-:1]#[C-:2].[Li+].[Li+].[C:5]([O:9][C:10]([N:12]1[CH2:17][CH2:16][CH:15]([CH3:18])[CH:14]([CH2:19]OS(C2C=CC(C)=CC=2)(=O)=O)[CH2:13]1)=[O:11])([CH3:8])([CH3:7])[CH3:6]>CS(C)=O>[C:5]([O:9][C:10]([N:12]1[CH2:17][CH2:16][CH:15]([CH3:18])[CH:14]([CH2:19][C:1]#[CH:2])[CH2:13]1)=[O:11])([CH3:6])([CH3:7])[CH3:8]

Participants

4

Reactant 2

HCID 86650159HCID 86650159, compoundHCID 178462446HCID 178462446, compound

Product 1

HCID 86650158HCID 86650158, compound

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Conditions

Temperature
8 °C

Procedure

A flask containing lithium acetylide, ethylene diamine complex (3.82 g, 37.4 mmol) was taken up in dry DMSO (50 mL) and cooled to approximately 8° C. (dilute ice bath) under argon atmosphere. To the cooled mixture was added a solution of (+/−)-4-methyl-3-(toluene-4-sulfonyloxymethyl)-piperidine-1-carboxylic acid tert-butyl ester (6.91 g, 17.79 mmol) in dry DMSO (40 mL), via slow drop-wise addition. The dark brown-black mixture was stirred vigorously to ambient temperature for 4.5 hours. The reaction was carefully quenched via the addition of a saturated solution of aqueous ammonium chloride (60 mL), followed by the addition of diethyl ether (120 mL) and water (50 mL). The mixture was transferred to a separatory funnel and shaken. The ether phase was collected and shaken with an equal volume of brine. The aqueous phases were back extracted with diethyl ether (2×100 mL). The crude was taken up in methylene chloride (40 mL) and adsorbed onto 25 g of silica gel. The solvent was stripped and the crude material was purified by silica gel chromatography, eluting with 4% to 20% ethyl acetate in hexanes, providing 2.21 g of (+/−)-4-methyl-3-prop-2-ynyl-piperidine-1-carboxylic acid tert-butyl ester as a clear mobile oil. MS (M+Na)+=260.

Workup

  1. additionvia slow drop-wise addition
  2. customThe reaction was carefully quenched via the addition of a saturated solution of aqueous ammonium chloride (60 mL)
  3. additionfollowed by the addition of diethyl ether (120 mL) and water (50 mL)
  4. customThe mixture was transferred to a separatory funnel
  5. stirringshaken
  6. customThe ether phase was collected
  7. stirringshaken with an equal volume of brine
  8. extractionThe aqueous phases were back extracted with diethyl ether (2×100 mL)
  9. customthe crude material was purified by silica gel chromatography
  10. washeluting with 4% to 20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-8bd15a0823274ed8ad1a61004bad38b1
Source dataset
uspto-grants-2013_01
Patent number
US08361962B2

Reaction notes

Loading…