Allyl bromide → Tert-butyl 4-((allyloxy)methyl)-4-methylpiperidine-1-carboxylate

HRID 1400783Notes

Reaction equation

HRID 1400783 reaction equation
[OH:1][CH2:2][C:3]1([CH3:16])[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH2:4]1.[H-].[Na+].Br[CH2:20][CH:21]=[CH2:22]>CC(N(C)C)=O>[CH2:22]([O:1][CH2:2][C:3]1([CH3:16])[CH2:8][CH2:7][N:6]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:5][CH2:4]1)[CH:21]=[CH2:20]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 24758Sodium hydrideHCID 232828431-Boc-4-(hydroxymethyl)-4-methylpiperidine

Product 1

HCID 86710836Tert-butyl 4-((allyloxy)methyl)-4-methylpiperidine-1-carboxylateYield 83.7%

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Procedure

To a solution of e tert-butyl 4-(hydroxymethyl)-4-methylpiperidine-1-carboxylate (479 mg, 2.089 mmol) in DMA (3 mL) was added 60 wt % sodium hydride (125 mg, 3.13 mmol). Reaction immediately turned yellow. Stirred for 5 min and added 3-bromoprop-1-ene (1263 mg, 10.44 mmol). After 3 h, partitioned between EtOAc and sat.aq.NH4Cl. The organic phase was washed with water (3×), brine and dried (MgSO4), filtered, and concentrated to give 471 mg (75%) of tert-butyl 4-((allyloxy)methyl)-4-methylpiperidine-1-carboxylate as a colorless oil. 1H NMR (400 MHz, CDCl3) δ 5.91 (ddt, J=17.2, 10.5, 5.3 Hz, 1H), 5.29 (dq, J=17.1, 1.7 Hz, 1H), 5.19 (dq, J=10.4, 1.5 Hz, 1H), 3.98 (dt, J=5.3, 1.5 Hz, 2H), 3.62 (br. s., 2H), 3.23-3.14 (m, 4H), 1.56-1.49 (m, 2H), 1.48 (s, 9H), 1.37-1.28 (m, 2H), 1.02 (s, 3H). LCMS (M+1)=270.25.

Workup

  1. customReaction immediately turned yellow
  2. waitAfter 3 h
  3. custompartitioned between EtOAc and sat.aq
  4. washThe organic phase was washed with water (3×), brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-e57005f1ce4e4705ad4b8e1660aab6aa
Source dataset
uspto-grants-2014_12
Patent number
US08906929B2

Reaction notes

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