Thiophenol → (3R,6S)-3-(allyloxyamino)-6-((tert-butyldimethylsilyloxy)methyl)-1,2,3,6-tetrahydropyridine-4-carboxamide

HRID 627142Notes

Reaction equation

HRID 627142 reaction equation
[CH2:1]([O:4][N:5]([C@@H:21]1[C:26]([C:27]([NH2:29])=[O:28])=[CH:25][C@@H:24]([CH2:30][O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33])[NH:23][CH2:22]1)S(C1C=CC([N+]([O-])=O)=CC=1[N+]([O-])=O)(=O)=O)[CH:2]=[CH2:3].C(=O)([O-])[O-].[Cs+].[Cs+].C1(S)C=CC=CC=1>C1COCC1>[CH2:1]([O:4][NH:5][C@@H:21]1[C:26]([C:27]([NH2:29])=[O:28])=[CH:25][C@@H:24]([CH2:30][O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:33])[CH3:34])[NH:23][CH2:22]1)[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 7969ThiophenolHCID 10796Cesium carbonateHCID 89852509(3R,6S)-3-(N-(allyloxy)-2,4-dinitrophenylsulfonamido)-6-((tert-butyldimethylsilyloxy)methyl)-1,2,3,6-tetrahydropyridine-4-carboxamide2×

Product 1

HCID 89852545(3R,6S)-3-(allyloxyamino)-6-((tert-butyldimethylsilyloxy)methyl)-1,2,3,6-tetrahydropyridine-4-carboxamideYield 80%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a reddish-brown, stirred suspension of (3R,6S)-3-(N-(allyloxy)-2,4-dinitrophenylsulfonamido)-6-((tert-butyldimethylsilyloxy)methyl)-1,2,3,6-tetrahydropyridine-4-carboxamide (Intermediate 106, 1.1 g, 1.9 mmol) and cesium carbonate (3.1 g, 9.5 mmol) in THF (about 45 mL), at ambient temperature under a blanket of argon, was added benzenethiol (polymer-bound reagent, 1.55 mmol/g) (4.5 g, 7.0 mmol). This mixture was stirred overnight at ambient temperature. Analysis by LCMS in the morning indicated complete consumption of starting material, as did analysis by TLC (5% methanol in methylene chloride). The mixture was filtered and the filtered material was rinsed with THF until no material remained that was responsive to UV or I2 stain on a silica plate. The red-orange solution obtained was concentrated and redissolved in methylene chloride. Normal-phase chromatography (0-6% methanol in methylene chloride, 80-g, 25 min.) afforded the desired compound (510 mg, 80%, orange-brown solid).

Workup

  1. stirringThis mixture was stirred overnight at ambient temperature
  2. customconsumption of starting material
  3. filtrationThe mixture was filtered
  4. washthe filtered material was rinsed with THF until no material
  5. customThe red-orange solution obtained
  6. concentrationwas concentrated
  7. dissolutionredissolved in methylene chloride

Sources & evidence

ORD record
ord-5552113df67c4ad3938971d83c55fd49
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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