Triacetoxyperiodinane → Tert-butyl 4-(4-methoxyphenyl)-3-oxopiperidine-1-carboxylate

HRID 1507256Notes

Reaction equation

HRID 1507256 reaction equation
[OH:1][C@@H:2]1[C@@H:7]([C:8]2[CH:13]=[CH:12][C:11]([O:14][CH3:15])=[CH:10][CH:9]=2)[CH2:6][CH2:5][N:4]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:3]1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl>[CH3:15][O:14][C:11]1[CH:10]=[CH:9][C:8]([CH:7]2[CH2:6][CH2:5][N:4]([C:16]([O:18][C:19]([CH3:21])([CH3:20])[CH3:22])=[O:17])[CH2:3][C:2]2=[O:1])=[CH:13][CH:12]=1

Participants

4

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 57240152(3R,4R)-tert-butyl 3-hydroxy-4-(4-methoxyphenyl)piperidine-1-carboxylate

Product 1

HCID 54595992Tert-butyl 4-(4-methoxyphenyl)-3-oxopiperidine-1-carboxylateYield 87%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (3R,4R)-tert-butyl 3-hydroxy-4-(4-methoxyphenyl)piperidine-1-carboxylate (180 mg, 0.59 mmol) in DCM (3 mL) at 0° C. under N2 was added Dess-Martin Periodinane (373 mg, 0.88 mmol). The mixture was allowed to warm to rt and stirred for 3 h. The reaction mixture was directly purified via silica gel chromatography eluting with 30% EtOAc in hexanes to afford tert-butyl 4-(4-methoxyphenyl)-3-oxopiperidine-1-carboxylate (155 mg, 87% yield). Subsequent results revealed that the 4R stereochemistry is lost in this reaction and the racemic product was obtained. 1H NMR (500 MHz, chloroform-d) δ 7.09-7.03 (m, 2H), 6.93-6.87 (m, 2H), 4.24 (d, J=18.0 Hz, 1H), 4.11-4.02 (m, 1H), 3.80 (s, 3H), 3.61 (dd, J=11.9, 5.6 Hz, 1H), 3.56-3.46 (m, 1H), 2.34-2.16 (m, 2H), 1.50 (s, 9H).

Workup

  1. customThe reaction mixture was directly purified via silica gel chromatography
  2. washeluting with 30% EtOAc in hexanes

Sources & evidence

ORD record
ord-891576ade5f34c6eab9089663e28c381
Source dataset
uspto-grants-2015_12
Patent number
US09221796B2

Reaction notes

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