Sulfuric Acid → (2S,5R)-benzyl 5-(benzyloxyamino)piperidine-2-carboxylate

HRID 508453Notes

Reaction equation

HRID 508453 reaction equation
S(=O)(=O)(O)O.[BH4-].[Na+].[CH2:8]([O:15][C:16]([C@@H:18]1[CH2:23][CH2:22][C:21](=[N:24][O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[CH2:20][NH:19]1)=[O:17])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.C12(CS(O)(=O)=O)C(C)(C)C(CC1)CC2=O>O1CCCC1>[CH2:8]([O:15][C:16]([C@@H:18]1[CH2:23][CH2:22][C@@H:21]([NH:24][O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[CH2:20][NH:19]1)=[O:17])[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 18462Bicyclo[2.2.1]heptane-1-methanesulfonic acid, 7,7-dimethyl-2-oxo-, (1S)-HCID 4311764Sodium borohydrideHCID 86702281Phenylmethyl (2S)-5-[(phenylmethoxy)imino]-2-piperidinecarboxylate

Product 1

HCID 70673934(2S,5R)-benzyl 5-(benzyloxyamino)piperidine-2-carboxylateYield 74%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Under nitrogen atmosphere, tetrahydrofuran (3 ml) and sulfuric acid (0.151 g, 1.53 mmol) were added to sodium borohydride (0.101 g, 2.66 mmol). The obtained mixture was added dropwise at −10° C. to the mixture consisting of (2S)-5-benzyloxyimino-piperidine-2-carboxylic acid benzyl ester (0.168 g, 0.50 mmol), (+)-camphorsulfonic acid (0.695 g, 2.99 mmol) and tetrahydrofuran (2 ml) for 0.5 hour. After 22 hours of stirring, the obtained reaction mixture was analyzed with high performance liquid chromatography to find that the reaction mixture contained 0.125 g of the title compound, and the reduction reaction proceeded with yield of 74%. The diastereo selectivity was (2S,5R)/(2S,5S)=81.4/18.6 (62.8% de).

Workup

  1. additionThe obtained mixture was added dropwise at −10° C. to the mixture
  2. customthe obtained reaction mixture

Sources & evidence

ORD record
ord-bec93985e49343e5bd4a5c757b75540b
Source dataset
uspto-grants-2015_08
Patent number
US09096523B2

Reaction notes

Loading…