Hydroxylamine → tert-butyl (2R)-2-[[2-[tert-butyl(dimethyl)silyl]oxy-1-[4-[(Z)-N'-hydroxycarbamimidoyl]phenyl]ethyl]amino]propanoate

HRID 572586Notes

Reaction equation

HRID 572586 reaction equation
[Si:1]([O:8][CH2:9][CH:10]([NH:19][C@@H:20]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH3:21])[C:11]1[CH:16]=[CH:15][C:14]([C:17]#[N:18])=[CH:13][CH:12]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[NH2:29][OH:30]>C(O)C>[NH2:18]/[C:17](=[N:29]\[OH:30])/[C:14]1[CH:13]=[CH:12][C:11]([CH:10]([NH:19][C@@H:20]([C:22]([O:24][C:25]([CH3:27])([CH3:26])[CH3:28])=[O:23])[CH3:21])[CH2:9][O:8][Si:1]([C:4]([CH3:7])([CH3:5])[CH3:6])([CH3:3])[CH3:2])=[CH:16][CH:15]=1

Participants

4

Reactant 2

HCID 787HydroxylamineHCID 66652924tert-butyl N-[2-{[tert-butyl(dimethyl)silyl]oxy}-1-(4-cyanophenyl)ethyl]-D-alaninate

Product 1

HCID 87091183tert-butyl (2R)-2-[[2-[tert-butyl(dimethyl)silyl]oxy-1-[4-[(Z)-N'-hydroxycarbamimidoyl]phenyl]ethyl]amino]propanoateYield 93.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of tert-butyl N-[2-{[tert-butyl(dimethyl)silyl]oxy}-1-(4-cyanophenyl)ethyl]-D-alaninate (2 g, 0.0049 mol) in Ethanol (40 ml) was added 50% aqueous Hydroxylamine (1.63 ml, 0.0247 mol) at RT. The reaction mixture was heated at 70° C. for 6 h, cooled to RT and concentrated under reduced pressure. The residue was dissolved in ethyl acetate, washed with water, brine, dried over Na2SO4 and evaporated to afford (2 g, 90%) of the title compound as brown oil. 1H NMR: (DMSO-d6, 400 MHz) δ 9.57 (s, 1H), 7.61-7.59 (d, J=8.3 Hz, 2H), 7.30-7.28 (d, J=8.3 Hz, 2H), 5.76-5.74 (d, J=5.00 Hz, 2H), 4.77-4.74 (m, 1H), 3.21-3.19 (m, 1H), 2.69-2.59 (m, 1H), 1.95-1.72 (m, 1H), 1.39 (s, 9H), 1.10-1.06 (m, 3H), 0.86-0.82 (m, 9H), 0.03 (s, 3H), −0.12 (s, 3H). LC/MS (Method A): 438.3 (M+H)+. HPLC (Method A) Rt 3.82 min. (Purity: 71.1%).

Workup

  1. temperaturecooled to RT
  2. concentrationconcentrated under reduced pressure
  3. dissolutionThe residue was dissolved in ethyl acetate
  4. washwashed with water, brine
  5. dry with materialdried over Na2SO4
  6. customevaporated

Sources & evidence

ORD record
ord-4f61b7992cb8405396d4a29e6679db94
Source dataset
uspto-grants-2015_05
Patent number
US09029405B2

Reaction notes

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