Sodium Carbonate → tert-Butyl 4-(4-nitrophenyl)-2,3-dihydro-1H-pyrrole-1-carboxylate

HRID 1485270Notes

Reaction equation

HRID 1485270 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[CH2:26][CH2:27][N:28]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH:29]=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:26]2[CH2:25][CH2:29][N:28]([C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[CH:27]=2)=[CH:12][CH:11]=1)([O-:9])=[O:8]

Participants

8

Reactant 4

HCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 27735524-Nitrophenylboronic acidHCID 86675729tert-butyl 4-(((trifluoromethyl)sulfonyl)oxy)-2,3-dihydro-1H-pyrrole-1-carboxylate

Product 1

HCID 71209487tert-Butyl 4-(4-nitrophenyl)-2,3-dihydro-1H-pyrrole-1-carboxylate

Reagents, catalysts & solvents 3

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

Conditions

Temperature
85 °C

Procedure

A solution of 2 M aqueous Na2CO3 (5.70 mL, 9.09 mmol) was added to a degassed mixture of 4-nitrophenylboronic acid (0.909 g, 1.52 mmol, 1.2 eq), tert-butyl 4-(((trifluoromethyl)sulfonyl)oxy)-2,3-dihydro-1H-pyrrole-1-carboxylate (I34 and 135) (1.44 g, 4.54 mmol), LiCl (0.385 g, 9.08 mmol) and Pd(PPh3)4 (1.57 g, 1.36 mmol) in 1,4-dioxane (10 mL). The reaction mixture was stirred at 80-90° C. for 4 hours. The resulting mixture was dissolved in EtOAc (70 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 give a mixture of the title compounds (1134 and 1135) (0.442 g, 34%) as a light yellow solid; 1H NMR (400 MHz, CDCl3) δ 8.41-8.32 (m, 2H), 8.24-8.19 (m, 2H), 7.81-7.73 (m, 2H), 7.52 (dd, J=8.8, 2.4 Hz), 6.43-6.33 (m, 1H), 4.58-4.48 (m, 4H), 4.42-4.31 (m, 4H), 1.52 (s, 9H), 1.51 (s, 9H).

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.)
  5. customto give

Sources & evidence

ORD record
ord-c263d16892234e219ea47311a0f73eb1
Source dataset
uspto-grants-2016_08
Patent number
US09421205B2

Reaction notes

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