Triphenylphosphine → Methyl 3-fluoro-2-formylpyridine-4-carboxylate

HRID 1426286Notes

Reaction equation

HRID 1426286 reaction equation
[O:1]=[O+][O-].[F:4][C:5]1[C:14]([CH:15]=C)=[N:13][CH:12]=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[F:4][C:5]1[C:14]([CH:15]=[O:1])=[N:13][CH:12]=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 24823Ozone2×HCID 696727743-Fluoro-2-vinyl-isonicotinic acid methyl ester

Product 1

HCID 86666496Methyl 3-fluoro-2-formylpyridine-4-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Ozone was bubbled through a solution of methyl 3-fluoro-2-vinylisonicotinate (1.4 g, 7.73 mmol, from Step 2) in methylene chloride (100 mL) at −78° C. until the blue color of excess ozone persisted. Nitrogen was bubbled through the solution for 1 minute to purge excess ozone and then triphenylphosphine (3.9 g, 15 mmol) was added and the solution was warmed to room temperature and stirred overnight. The compound was dry loaded onto silica gel. Flash chromatography eluting with 40% ethyl acetate in hexanes afforded product (0.8 g, 57%) as an off-white crystalline solid. 1H NMR (300 MHz, CDCl3): δ 10.27 (s, 1H), 8.73 (d, 1H), 8.01 (dd, 1H), 4.01 (s, 3H).

Workup

  1. customNitrogen was bubbled through the solution for 1 minute
  2. customto purge excess ozone
  3. customThe compound was dry
  4. washFlash chromatography eluting with 40% ethyl acetate in hexanes afforded product (0.8 g, 57%) as an off-white crystalline solid

Sources & evidence

ORD record
ord-d70aede932974ef28b9e4567297aed72
Source dataset
uspto-grants-2015_01
Patent number
US08933085B2

Reaction notes

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