Benzyl Bromide → 2-Benzyl-5-[1,3]dioxolan-2-yl-pyridine

HRID 1891962

Reaction equation

HRID 1891962 reaction equation
[CH2:1](Br)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[C:10]1[CH:15]=[CH:14][C:13]([CH:16]2[O:20][CH2:19][CH2:18][O:17]2)=[CH:12][N:11]=1>[Zn].[Ni](Cl)Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O1CCCC1>[CH2:1]([C:10]1[CH:15]=[CH:14][C:13]([CH:16]2[O:17][CH2:18][CH2:19][O:20]2)=[CH:12][N:11]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 7498Benzyl BromideHCID 184696682-Bromo-5-(1,3-dioxolan-2-YL)pyridine

Product 1

HCID 592551082-Benzyl-5-[1,3]dioxolan-2-yl-pyridineYield 62%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 498315Nickel, dichlorobis(triphenylphosphine)-CatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

To a suspension of zinc (5.0 g, 77 mmol, highly reactive Rieke metal, 100 mL tetrahydrofuran suspension) and tetrahydrofuran (300 mL) was added dropwise benzyl bromide (7.9 mL, 66 mmol) at 0° C., which was stirred for 4 hours at the same temperature. To this suspension were added bis(triphenylphosphine) nickel (II) chloride (5.8 g, 8.8 mmol) and 2-bromo-5-[1,3]dioxolan-2-yl-pyridine (11 g, 49 mmol) described in Manufacturing Example 210-1-2, which was stirred for another 2 hours at room temperature. The reaction solution was partitioned into ethyl acetate and an ammonium chloride aqueous solution. The organic layer was separated and concentrated under a reduced pressure. The residue was purified by silica gel column chromatography (heptane:ethyl acetate=2:1, 1:1) to obtain the title compound (7.3 g, 62%).

Workup

  1. stirringwas stirred for another 2 hours at room temperature
  2. customThe reaction solution was partitioned into ethyl acetate
  3. customThe organic layer was separated
  4. concentrationconcentrated under a reduced pressure
  5. customThe residue was purified by silica gel column chromatography (heptane:ethyl acetate=2:1, 1:1)

Sources & evidence

ORD record
ord-6dc17e9fdc8a4d419d504261b55ba2b8
Source dataset
uspto-grants-2013_08
Patent number
US08507530B2

Linked notes

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