1-Bromo-3,4-(methylenedioxy)benzene → HCID 89677540, compound

HRID 2278156Notes

Reaction equation

HRID 2278156 reaction equation
Br[C:2]1[CH:10]=[CH:9][C:5]2[O:6][CH2:7][O:8][C:4]=2[CH:3]=1.[C:11]([Li])([CH3:14])([CH3:13])C.[N:16]1([C:27]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:28])[CH2:21][CH2:20][CH:19]([C:22]([O:24]CC)=O)[CH2:18][CH2:17]1>C1COCC1>[O:6]1[C:5]2[CH:9]=[CH:10][C:2]([C:22]([C:13]3[CH:11]=[CH:14][C:4]4[O:8][CH2:7][O:6][C:5]=4[CH:9]=3)([OH:24])[CH:19]3[CH2:18][CH2:17][N:16]([C:27]([O:29][C:30]([CH3:31])([CH3:32])[CH3:33])=[O:28])[CH2:21][CH2:20]3)=[CH:3][C:4]=2[O:8][CH2:7]1

Participants

5

Reactant 3

HCID 758311-Bromo-3,4-(methylenedioxy)benzeneHCID 27588121-Tert-butyl 4-ethyl piperidine-1,4-dicarboxylateHCID 178418306HCID 178418306, compound

Product 1

HCID 89677540HCID 89677540, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirring solution of 5-bromobenzo-1,3-dioxole (1.77 g, 8.8 mmol) in dry THF (10 mL) at −78° C. under N2 was added tert-butyllithium (10.5 mL, 17.9 mmol, 1.7M in pentane). After 2 h, 1-tert-butyl 4-ethyl piperidine-1,4-dicarboxylate (1.13 g, 4.4 mmol) was added dropwise to the reaction mixture at −78° C. and stirred for 1 h. The reaction mixture was subsequently warmed to room temperature and stirred overnight. The reaction was quenched with saturated aqueous NH4Cl (30 mL) and the aqueous layer extracted with EtOAc (3×30 mL). The combined organic layers were dried over Na2SO4 and concentrated under reduced pressure. The mixture was purified by flash chromatography (10-30% EtOAc/hexanes) to give tert-butyl 4-(bis(benzo[d][1,3]dioxol-5-yl)(hydroxy)methyl)piperidine-1-carboxylate as a white solid (1.3 g, 73%): 1H NMR 500 MHz (CDCl3) δ 6.93-6.89 (m, 4H), 6.73 (d, J=8.0 Hz, 2H), 5.91 (s, 4H), 4.14 (bs, 2H), 2.74-2.63 (m, 2H), 2.41-2.34 (m, 1H), 2.04 (s, 1H), 1.55-1.47 (m, 2H), 1.43 (s, 9H), 1.32-1.23 (m, 2H).

Workup

  1. stirringstirred overnight
  2. customThe reaction was quenched with saturated aqueous NH4Cl (30 mL)
  3. extractionthe aqueous layer extracted with EtOAc (3×30 mL)
  4. dry with materialThe combined organic layers were dried over Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customThe mixture was purified by flash chromatography (10-30% EtOAc/hexanes)

Sources & evidence

ORD record
ord-e0ef7f60a77e40a4b3fc17dca20dcbae
Source dataset
uspto-grants-2015_09
Patent number
US09133148B2

Reaction notes

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