2-Vinylpyridine → HCID 66837013, compound

HRID 872048Notes

Reaction equation

HRID 872048 reaction equation
[CH:1]([C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][N:4]=1)=[CH2:2].[N+](=[CH:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])=[N-]>C1(C)C=CC=CC=1>[N:4]1[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=1[C@@H:1]1[CH2:2][C@H:11]1[C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

4

Reactant 2

HCID 75212-VinylpyridineHCID 12192Ethyl diazoacetate

Product 1

HCID 66837013HCID 66837013, compoundYield 44%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 2-vinylpyridine (2 g, 19.02 mmol) in toluene (40 mL) was treated with ethyl diazoacetate (1.973 ml, 19.02 mmol) and stirred at reflux overnight. The mixture was concentrated in vacuo and the residue was purified by gradient elution on silica gel (0 to 50% EtOAc in hexanes) to elute peak 1; the solvent gradient was then ramped to 100% EtOAc to elute peak 2. This yielded the title compound (1.6 g, 44%) as the first eluting diastereomer, and the corresponding cis diastereomer (914 mg, 25%) as the second eluting diastereomer, both as yellow oils. Data for trans stereoisomer: 1H NMR δ (500 MHz, CDCl3): 8.44 (m, 1H), 7.56 (td, J=7.6, 1.7 Hz, 1H), 7.22 (dd, J=7.8, 1.0 Hz, 1H), 7.08 (ddd, J=7.6, 4.9, 1.2 Hz, 1H), 4.17 (q, J=7.3 Hz, 2H), 2.58 (ddd, J=10.0, 6.1, 3.9 Hz, 1H), 2.25 (ddd, J=9.5, 5.6, 3.9 Hz, 1H), 1.61, (m, 2H), 1.28 (t, J=7.1 Hz, 3H). LRMS (ES) calculated M+H for C11H13NO2S: 192.2. Found: 192.1. Enantiomers can be resolved by chiral preparative SFC (3.0 cm i.d.×25 cm ChiralTech IC, 7% EtOH/CO2, 70 mL/min) and analyzed by chiral analytical SFC (4.6 mm i.d.×25 cm ChiralTech IC, 7% EtOH/CO2, 2.4 mL/min) ent1=3.6 min, ent2=4.1 min.

Workup

  1. temperatureat reflux overnight
  2. concentrationThe mixture was concentrated in vacuo
  3. customthe residue was purified by gradient elution on silica gel (0 to 50% EtOAc in hexanes)
  4. washto elute peak 1
  5. washto elute peak 2

Sources & evidence

ORD record
ord-4758ec7045a04802b34bfc0bb3be3a40
Source dataset
uspto-grants-2015_03
Patent number
US08975261B2

Reaction notes

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