Phenyl triflimide → tert-Butyl 5-(((trifluoromethyl)sulfonyl)oxy)-3,4-dihydropyridine-1(2H)-carboxylate

HRID 708291Notes

Reaction equation

HRID 708291 reaction equation
C([N-]C(C)C)(C)C.[Li+].[C:9]([O:13][C:14]([N:16]1[CH2:21][CH2:20][CH2:19][C:18](=[O:22])[CH2:17]1)=[O:15])([CH3:12])([CH3:11])[CH3:10].C1C=CC(N([S:37]([C:40]([F:43])([F:42])[F:41])(=[O:39])=[O:38])[S:30]([C:33]([F:36])([F:35])[F:34])(=[O:32])=[O:31])=CC=1>O1CCCC1>[C:9]([O:13][C:14]([N:16]1[CH2:17][C:18]([O:22][S:30]([C:33]([F:36])([F:35])[F:34])(=[O:32])=[O:31])=[CH:19][CH2:20][CH2:21]1)=[O:15])([CH3:12])([CH3:10])[CH3:11].[C:9]([O:13][C:14]([N:16]1[CH:17]=[C:18]([O:22][S:37]([C:40]([F:41])([F:42])[F:43])(=[O:38])=[O:39])[CH2:19][CH2:20][CH2:21]1)=[O:15])([CH3:12])([CH3:10])[CH3:11]

Participants

6

Reactant 3

HCID 142176Phenyl triflimideHCID 2724682Lithium diisopropylamideHCID 2756825Tert-butyl 3-oxopiperidine-1-carboxylate

Product 2

HCID 10980453tert-Butyl 5-(((trifluoromethyl)sulfonyl)oxy)-3,4-dihydropyridine-1(2H)-carboxylateHCID 53978067tert-Butyl 3-(((trifluoromethyl)sulfonyl)oxy)-5,6-dihydropyridine-1(2H)-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of lithium diisopropylamide (0.0144 mol, 2M in heptane/THF/EtPh, 7.2 mL) in tetrahydrofuran (25 mL) at −78° C. was added a solution of 3-Oxo-piperidine-1-carboxylic acid tert-butyl ester (2.00 g, 0.0100 mol) in tetrahydrofuran (5 mL) dropwise. After 15 minutes, N-phenylbis(trifluoromethanesulphonimide) (4.303 g, 0.01204 mol) in tetrahydrofuran (10 mL) was added. The reaction was slowly warmed to room temperature and stirred overnight. The reaction was cooled to 0° C. and quenched with saturated NH4Cl, diluted with water, and extracted 3 times with dichloromethane. The organic layers were combined, dried with MgSO4, and concentrated. The mixture was purified by flash chromatography (EtOAc/hexanes) to give 0.933 g of 5-Trifluoromethanesulfonyloxy-3,6-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester and 1.1234 g of 5-Trifluoromethanesulfonyloxy-3,4-dihydro-2H-pyridine-1-carboxylic acid tert-butyl ester.

Workup

  1. temperatureThe reaction was cooled to 0° C.
  2. customquenched with saturated NH4Cl
  3. additiondiluted with water
  4. extractionextracted 3 times with dichloromethane
  5. dry with materialdried with MgSO4
  6. concentrationconcentrated
  7. customThe mixture was purified by flash chromatography (EtOAc/hexanes)

Sources & evidence

ORD record
ord-8efd725b23b64153b1a335513d85fed1
Source dataset
uspto-grants-2015_11
Patent number
US09175009B2

Reaction notes

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