Benzyl carbamate → Benzyl (3-oxocyclohexyl)carbamate

HRID 1776227Notes

Reaction equation

HRID 1776227 reaction equation
[C:1]1(=[O:7])[CH2:6][CH2:5][CH2:4][CH:3]=[CH:2]1.[C:8](=[O:18])([O:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[NH2:9]>C(Cl)Cl.CC#N.CC#N.Cl[Pd]Cl>[O:7]=[C:1]1[CH2:6][CH2:5][CH2:4][CH:3]([NH:9][C:8](=[O:18])[O:10][CH2:11][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)[CH2:2]1

Participants

5

Reactant 2

HCID 12136Benzyl carbamateHCID 135942-Cyclohexen-1-one

Product 1

HCID 10171453Benzyl (3-oxocyclohexyl)carbamateYield 77.6%

Reagents, catalysts & solvents 2

HCID 6093782Bis(acetonitrile)dichloropalladiumCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 2-cyclohexen-1-one (1.442 g, 15.0 mmol) in anhydrous methylene chloride (15 mL) was added bis(acetonitrile)dichloro-palladium(II) (0.231 g, 1.0 mmol) and benzyl carbamate (1.497 g, 9.9 mmol) and stirred under nitrogen for 24 hrs. The reaction mixture was filtered through a pad of silica gel, washing with ethyl acetate, and concentrated in vacuo. The crude product was purified by silica gel chromatography (20-65% ethyl acetate/hexanes) to give a pale yellow low melting solid (1.9 g). 1H NMR (300 MHz, CDCl3) δ 7.34 (m, 5H), 5.09 (s, 2H), 4.81 (br s, 1H), 3.99 (br s, 1H), 2.73 (m, 1H), 2.36-2.26 (m, 3H), 2.11-1.97 (m, 2H), 1.67-1.64 (m, 2H). ESI m/z: 248.0 (M+H).

Workup

  1. filtrationThe reaction mixture was filtered through a pad of silica gel
  2. washwashing with ethyl acetate
  3. concentrationconcentrated in vacuo
  4. customThe crude product was purified by silica gel chromatography (20-65% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-2aa668e1189442c3ae11bcdecb78cafc
Source dataset
uspto-grants-2016_02
Patent number
US09265772B2

Reaction notes

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