2,6-Lutidine → HCID 90402594, compound

HRID 1049270Notes

Reaction equation

HRID 1049270 reaction equation
[C:1]([C:3]1[CH:8]=[C:7]([O:9][C:10]2[C:11]([CH3:19])=[N:12][C:13]([N+:16]([O-:18])=[O:17])=[CH:14][CH:15]=2)[CH:6]=[CH:5][N:4]=1)#[CH:2].[C:20]([O:26][CH2:27][N:28]=[N+:29]=[N-:30])(=[O:25])[C:21]([CH3:24])([CH3:23])[CH3:22].N1C(C)=CC=CC=1C>C(O)(C)(C)C.CC#N.[Cu]I>[C:20]([O:26][CH2:27][N:28]1[CH:2]=[C:1]([C:3]2[CH:8]=[C:7]([O:9][C:10]3[C:11]([CH3:19])=[N:12][C:13]([N+:16]([O-:18])=[O:17])=[CH:14][CH:15]=3)[CH:6]=[CH:5][N:4]=2)[N:30]=[N:29]1)(=[O:25])[C:21]([CH3:24])([CH3:23])[CH3:22]

Participants

7

Reactant 3

HCID 79372,6-LutidineHCID 11521126Azidomethyl 2,2-dimethylpropanoateHCID 90403368HCID 90403368, compound

Product 1

HCID 90402594HCID 90402594, compoundYield 84%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6342AcetonitrileSolventHCID 6386tert-ButanolSolvent

Procedure

A solution of 3-((2-ethynylpyridin-4-yl)oxy)-2-methyl-6-nitropyridine (0.2 g, 0.78 mmol) and azidomethyl pivalate (0.209 g, 1.33 mmol; See: Syn Lett. 2005, (18), 2847-2850) were combined in tert-butanol (3 mL) and treated with copper(I) iodide (0.030 g, 0.157 mmol) followed by a solution of 2,6-lutidine (0.091 mL, 0.78 mmol) in MeCN (3 mL) and the resultant mixture was stirred at RT for 3 h. The mixture was partitioned between water (30 mL) and EtOAc (30 mL). The aqueous layer was extracted with EtOAc and the combined organics were washed with brine, dried (Na2SO4) and concentrated. The crude product was purified by silica gel chromatography (EtOAc/Hex) to afford (4-(4-((2-methyl-6-nitropyridin-3-yl)oxy)pyridin-2-yl)-1H-1,2,3-triazol-1-yl)methyl pivalate (0.27 g, 84%) as an orange foam. 1H NMR (400 MHz, DMSO-d6): δ 8.74 (s, 1H), 8.60 (d, J=5.7 Hz, 1H), 8.26 (d, J=8.7 Hz, 1H), 7.94 (d, J=8.7 Hz, 1H), 7.64 (d, J=2.4 Hz, 1H), 7.12 (dd, J=5.6, 2.5 Hz, 1H), 6.37 (s, 2H), 2.50 (s, 3H), 1.11 (s, 9H); MS (ESI) m/z: 413.2 (M+H+).

Workup

  1. customThe mixture was partitioned between water (30 mL) and EtOAc (30 mL)
  2. extractionThe aqueous layer was extracted with EtOAc
  3. washthe combined organics were washed with brine
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customThe crude product was purified by silica gel chromatography (EtOAc/Hex)

Sources & evidence

ORD record
ord-93fd7d790ffc40eebecf334010ec69eb
Source dataset
uspto-grants-2016_07
Patent number
US09382228B2

Reaction notes

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