(3-Chlorophenyl)boronic acid → (S)-tert-butyl 1-(3-chlorophenyl)-2-oxoazepan-3-ylcarbamate

HRID 529515Notes

Reaction equation

HRID 529515 reaction equation
[O:1]=[C:2]1[C@@H:8]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:15])([CH3:14])[CH3:13])[CH2:7][CH2:6][CH2:5][CH2:4][NH:3]1.[Cl:17][C:18]1[CH:19]=[C:20](B(O)O)[CH:21]=[CH:22][CH:23]=1>C(Cl)Cl.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[Cl:17][C:18]1[CH:23]=[C:22]([N:3]2[CH2:4][CH2:5][CH2:6][CH2:7][C@H:8]([NH:9][C:10](=[O:16])[O:11][C:12]([CH3:13])([CH3:15])[CH3:14])[C:2]2=[O:1])[CH:21]=[CH:20][CH:19]=1

Participants

5

Reactant 2

HCID 2734323(3-Chlorophenyl)boronic acidHCID 7022178(S)-tert-Butyl (2-oxoazepan-3-yl)carbamate

Product 1

HCID 68310942(S)-tert-butyl 1-(3-chlorophenyl)-2-oxoazepan-3-ylcarbamateYield 10.1%

Reagents, catalysts & solvents 2

HCID 8895Cupric acetateCatalystHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of (S)-tert-butyl 2-oxoazepan-3-ylcarbamate (400 mg, 1.75 mmol) in DCM (7.5 mL) was added TEA (0.488 mL, 3.50 mmol) followed by copper (II) acetate (477 mg, 2.63 mmol) and 3-chlorophenylboronic acid (548 mg, 3.50 mmol) at rt under argon. Then, activated molecular sieves (˜1 gm) were added. The reaction mixture was stirred at rt for 36 hr. The reaction mixture was filtered through CELITE®. The filtrate was concentrated. The residue was purified using silica gel chromatography (ISCO system) eluting with a gradient of 0-100% EtOAc/Hex to give (S)-tert-butyl 1-(3-chlorophenyl)-2-oxoazepan-3-ylcarbamate (60.0 mg, 0.177 mmol, 10.1% yield) as white solid. Anal. Calcd. for C17H23ClN2O3 m/z 338.8. found: 339.1 (M+H)+.

Workup

  1. additionThen, activated molecular sieves (˜1 gm) were added
  2. filtrationThe reaction mixture was filtered through CELITE®
  3. concentrationThe filtrate was concentrated
  4. customThe residue was purified
  5. washeluting with a gradient of 0-100% EtOAc/Hex

Sources & evidence

ORD record
ord-fa80b290111547e1aacba867658871ab
Source dataset
uspto-grants-2016_05
Patent number
US09346852B2

Reaction notes

Loading…