4-Nitrobenzyl chloroformate → HCID 18677664, compound

HRID 370000Notes

Reaction equation

HRID 370000 reaction equation
[CH2:1]([NH:4][CH:5]1[CH2:10][CH2:9][N:8]([C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])[CH2:7][CH2:6]1)[CH:2]=[CH2:3].C(N(CC)C(C)C)(C)C.Cl[C:28]([O:30][CH2:31][C:32]1[CH:37]=[CH:36][C:35]([N+:38]([O-:40])=[O:39])=[CH:34][CH:33]=1)=[O:29]>ClCCl.C(OCC)(=O)C>[C:14]([O:13][C:11]([N:8]1[CH2:7][CH2:6][CH:5]([N:4]([CH2:1][CH:2]=[CH2:3])[C:28]([O:30][CH2:31][C:32]2[CH:33]=[CH:34][C:35]([N+:38]([O-:40])=[O:39])=[CH:36][CH:37]=2)=[O:29])[CH2:10][CH2:9]1)=[O:12])([CH3:17])([CH3:16])[CH3:15]

Participants

6

Reactant 3

HCID 782054-Nitrobenzyl chloroformateHCID 81531DiisopropylethylamineHCID 18677683tert-Butyl 4-[(prop-2-en-1-yl)amino]piperidine-1-carboxylate

Product 1

HCID 18677664HCID 18677664, compoundYield 82.1%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A portion of the crude 4-(allylamino)-1-(tert-butoxycarbonyl)piperidine (400 mg, 1.66 mmol) was dissolved in 10 mL of dichloromethane and treated with N,N-diisopropylethylamine (0.700 mL, 519 mg, 4.0 mmol) and 4-nitrobenzyl chloroformate (392 mg, 1.82 mmol). After stirring 3 h at RT, the mixture was diluted with 30 mL of ethyl acetate and washed with 15 mL each of 2 N aqueous HCl, saturated aqueous sodium bicarbonate, and brine. The organic layer was dried over sodium sulfate, and evaporated. The residue was purified by flash column chromatography on silica gel, eluting with 30% ethyl acetate in hexane, to give 572 mg of the title compound as a colorless syrup. 1H NMR (400 MHz, CDCl3): δ 8.22 (d, 2H, J=8 Hz), 7.50 (d, 2H, J=8 Hz), 5.80 (ddt, 1H, J=17, 10, 5 Hz), 5.23 (s, 2H), 5.18-5.09 (m, 2H), 4.27-4.08 (m, 3H), 3.89-3.79 (m, 2H), 2.79-2.66 (m, 2H), 1.74-1.52 (m, 4H), 1.46 (s, 9H). Mass spectrum (ESI): m/z=420 (M+1, 27%), 437 (M+1+NH3, 100%).

Workup

  1. washwashed with 15 mL each of 2 N aqueous HCl, saturated aqueous sodium bicarbonate, and brine
  2. dry with materialThe organic layer was dried over sodium sulfate
  3. customevaporated
  4. customThe residue was purified by flash column chromatography on silica gel
  5. washeluting with 30% ethyl acetate in hexane

Sources & evidence

ORD record
ord-7680d481acea4065bb6b07af4e39a795
Source dataset
uspto-grants-2000_10
Patent number
US06140349

Reaction notes

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