Sodium Carbonate → HCID 22049016, compound

HRID 1485174Notes

Reaction equation

HRID 1485174 reaction equation
C([O-])([O-])=O.[Na+].[Na+].[N+:7]([C:10]1[CH:15]=[CH:14][C:13](B(O)O)=[CH:12][CH:11]=1)([O-:9])=[O:8].FC(F)(F)S(O[C:25]1[CH2:30][CH2:29][N:28]([C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:27][CH:26]=1)(=O)=O.[Li+].[Cl-]>O1CCOCC1.CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[N+:7]([C:10]1[CH:15]=[CH:14][C:13]([C:25]2[CH2:30][CH2:29][N:28]([C:31]([O:33][C:34]([CH3:37])([CH3:36])[CH3:35])=[O:32])[CH2:27][CH:26]=2)=[CH:12][CH:11]=1)([O-:9])=[O:8]

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 27735524-Nitrophenylboronic acidHCID 10991161Tert-butyl 4-(trifluoromethanesulfonyloxy)-1,2,3,6-tetrahydropyridine-1-carboxylate

Product 1

HCID 22049016HCID 22049016, compoundYield 50%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
87.5 °C

Procedure

A solution of 2 M Na2CO3 (5.66 mL, 11.3 mmol) was added to a mixture of 4-nitrophenylboronic acid (0.831 g, 4.98 mmol), tert-butyl 4-(((trifluoromethyl)sulfonyl)oxy)-5,6-dihydropyridine-1(2H)-carboxylate (I42) (1.50 g, 4.53 mmol), LiCl (0.384 g, 9.06 mmol) and Pd(PPh3)4 (1.308 g, 1.132 mmol) in 1,4-dioxane (20 mL). The reaction mixture was stirred at 85-90° C. for 4 hours. The resulting mixture was dissolved in EtOAc (100 mL) and the organic layer was washed with H2O (50 mL), brine (50 mL) and dried over Na2SO4 to yield a dark red oil. The oil was purified by column chromatography on silica gel (0-20% EtOAc in petroleum benzine 40-60° C.) to yield the title compound (I43) (0.683 g, 50%) as a pale brown solid; 1H NMR (400 MHz, CDCl3) δ 8.24-8.16 (m, 2H), 7.55-7.47 (m, 2H), 6.23 (s, 1H), 4.14-4.12 (m, 2H), 3.66 (t, J=5.7 Hz, 2H), 2.55 (bs, 2H), 1.50 (s, 9H). LCMS Method C: rt 6.39 min; m/z 249 [M-Boc+2H]+, 205 [M-tButyl+2H]+.

Workup

  1. washthe organic layer was washed with H2O (50 mL), brine (50 mL)
  2. dry with materialdried over Na2SO4
  3. customto yield a dark red oil
  4. customThe oil was purified by column chromatography on silica gel (0-20% EtOAc in petroleum benzine 40-60° C.)

Sources & evidence

ORD record
ord-971924b17f94439694de87dbac6ef7a4
Source dataset
uspto-grants-2016_08
Patent number
US09421205B2

Reaction notes

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