Triphenylphosphine → HCID 86675415, compound

HRID 407244Notes

Reaction equation

HRID 407244 reaction equation
[O:1]=[O+][O-].[C:4]([O:8][C:9]([N:11]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[C:12]1[CH:17]=[C:16]([CH:18]=C)[N:15]=[C:14]([C:20]([O:22][CH3:23])=[O:21])[C:13]=1[O:24][CH3:25])=[O:10])([CH3:7])([CH3:6])[CH3:5].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[C:4]([O:8][C:9]([N:11]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[C:12]1[CH:17]=[C:16]([CH:18]=[O:1])[N:15]=[C:14]([C:20]([O:22][CH3:23])=[O:21])[C:13]=1[O:24][CH3:25])=[O:10])([CH3:5])([CH3:7])[CH3:6]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 24823OzoneHCID 86675414HCID 86675414, compound

Product 1

HCID 86675415HCID 86675415, compoundYield 72.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Ozone was bubbled through a solution of methyl 4-[bis(tert-butoxycarbonyl)amino]6-ethenyl-3-methoxypyridine-2-carboxylate (0.382 g, 0.935 mmol) in CH2Cl2 (9.35 ml) at −78° C. until the solution turned blue. Oxygen was bubbled through the reaction mixture until the solution turned yellow and triphenylphosphine (0.294 g, 1.122 mmol) was added. The reaction mixture was allowed to warm to room temperature and was stirred overnight. The reaction mixture was then adsorbed onto celite and the residue was purified by flash column chromatography (ISCO, SiO2 24 g, hexanes/EtOAc 100:0 to 0:100 gradient) to afford methyl 4-[bis(tert-butoxycarbonyl)amino]-6-formyl-3-methoxypyridine-2-carboxylate (279 mg, 0.680 mmol, 72.7% yield) as a light yellow oil. ESIMS m/z 411 ([M−H]+); 1H NMR (400 MHz, CDCl3) δ 10.03 (s, 1H), 7.88 (s, 1H), 4.05 (s, 3H), 3.95 (s, 3H), 1.43 (s, 18H).

Workup

  1. customOxygen was bubbled through the reaction mixture until the solution
  2. customthe residue was purified by flash column chromatography (ISCO, SiO2 24 g, hexanes/EtOAc 100:0 to 0:100 gradient)

Sources & evidence

ORD record
ord-fd97b5548d2940bf9c3ed3e3b294a6b9
Source dataset
uspto-grants-2014_06
Patent number
US08754229B2

Reaction notes

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