Methyl morpholine oxide → (+/-)-(2S,3R)-1-tert-Butyloxycarbonyl-3-(tert-butyldimethylsilanyloxy)-2-formylpiperidine

HRID 751161Notes

Reaction equation

HRID 751161 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][C@@H:10]([O:14][Si:15]([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16])[C@@H:9]1[CH2:22][OH:23])=[O:7])([CH3:4])([CH3:3])[CH3:2].C[N+]1([O-])CCOCC1>C(Cl)Cl.CCCCCC.CCC[N+](CCC)(CCC)CCC.[O-][Ru](=O)(=O)=O>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][C@@H:10]([O:14][Si:15]([C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:17])[CH3:16])[C@H:9]1[CH:22]=[O:23])=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 2

HCID 82029Methyl morpholine oxideHCID 68457794(+/-)-(2S,3R)-1-tert-Butoxycarbonyl-3-(tert-butyldimethylsilanyloxy)-2-hydroxymethylpiperidine

Product 1

HCID 86594307(+/-)-(2S,3R)-1-tert-Butyloxycarbonyl-3-(tert-butyldimethylsilanyloxy)-2-formylpiperidineYield 90%

Reagents, catalysts & solvents 3

HCID 178419074HCID 178419074, compoundCatalystHCID 6344DichloromethaneSolventHCID 8058HexaneSolvent

Procedure

To a solution of 77E (800 mg, 2.3 mmol) in DCM (15 mL) was added 4-methylmorpholine N-oxide (541 mg, 4.6 mmol, 2 equiv) followed by the addition of TPAP (177 mg, 0.5 mmol, 0.22 equiv). The mixture was stirred at rt for 3 h. The mixture was diluted with hexane (10 mL), loaded on a layer of silica gel and eluted with 25% EtOAc/hexane. The filtrate was concentrated to gave the desired product 77F (711 mg, 90%): Rf (30% EtOAc/hexane) 0.87; HPLC (Phenomenex Luna 5 u C18 4.6×50 mm, linear gradient over 4 min) retention time 4.1 min (100%); MS (ES) m/z 344.1 [M+1]+; HRMS calcd for C17H34NO4Si 344.2257, Found 344.2259.

Workup

  1. washeluted with 25% EtOAc/hexane
  2. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-0bd5b390afd24324982b66e905cc5c8c
Source dataset
uspto-grants-2008_07
Patent number
US07405234B2

Reaction notes

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