Allyl bromide → Tert-butyl 4-allyl-4-hydroxypiperidine-1-carboxylate

HRID 1386678Notes

Reaction equation

HRID 1386678 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11](=[O:14])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH2:15](Br)[CH:16]=[CH2:17]>C1COCC1.CCOC(C)=O.[Cl-].[Cl-].[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Ti+2].[Zn]>[C:1]([O:5][C:6]([N:8]1[CH2:9][CH2:10][C:11]([CH2:17][CH:16]=[CH2:15])([OH:14])[CH2:12][CH2:13]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 2

HCID 7841Allyl bromideHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylate

Product 1

HCID 21955339Tert-butyl 4-allyl-4-hydroxypiperidine-1-carboxylateYield 45.2%

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 124040768Titanocene dichiorideCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A dry round bottom flask was purged with nitrogen and charged with 1-t-butoxycarbonyl-4-piperidinone (20 g, 100 mmol), titanocene dichloride (1.2 g, 5 mmol) and zinc dust (7.8 g, 120 mmol) in 100 mL dry THF. Allyl bromide (11.3 mL, 130 mmol) was added and the mixture was stirred for 5 h at rt. The mixture was diluted with 700 mL EtOAc, washed with 2.0 M HCl (2×200 ML), 100 mL of sat'd NaCl, dried over MgSO4 and concentrated. Flash chromatography (650 g silica, 10/1 CH2Cl2/Et2O eluant) afforded 10.9 g (45%) of the title compound: 1H NMR (300 MHz) δ 1.4-1.6 (13H), 2.2-2.25 (d, 2H), 3.1-3.2 (m, 2H), 3.75-3.85 (m, 2H), 5.1-5.25 (m, 2H), 5.78-5.92 (m, 1H).

Workup

  1. customA dry round bottom flask was purged with nitrogen
  2. washwashed with 2.0 M HCl (2×200 ML), 100 mL of sat'd NaCl
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-885f026593fb4b5f9172ad43f8355b03
Source dataset
uspto-grants-2001_07
Patent number
US06265434B1

Reaction notes

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