4-Nitrobenzyl chloroformate → HCID 70152108, compound

HRID 1016597Notes

Reaction equation

HRID 1016597 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]([NH:4][CH2:1][CH:2]=[CH: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 70152108HCID 70152108, 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): δ8.22 (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-10fbfaacdb80438b88338593411b11c7
Source dataset
uspto-grants-2002_11
Patent number
US06476054B1

Reaction notes

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