N,N,N',N'-Tetramethylethylenediamine → HCID 86663616, compound

HRID 1748114Notes

Reaction equation

HRID 1748114 reaction equation
C([Li])CCC.CN(C)CCN(C)C.[N:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[NH:20]C(=O)OC(C)(C)C.B(OC(C)C)(OC(C)C)OC(C)C.C(=O)([O-])[O-].[K+].[K+].Br[C:48]1[CH:53]=[CH:52][C:51]([Br:54])=[CH:50][N:49]=1>C1COCC1.C1(C)C=CC=CC=1.CO.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>[Br:54][C:51]1[CH:52]=[CH:53][C:48]([C:16]2[C:15]([NH2:20])=[N:14][CH:19]=[CH:18][CH:17]=2)=[N:49][CH:50]=1

Participants

11

Reactant 6

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 11430Potassium CarbonateHCID 21531Triisopropyl borateHCID 693532,5-DibromopyridineHCID 112063492-(Boc-amino)pyridineHCID 178418339Butyllithium

Product 1

HCID 86663616HCID 86663616, compoundYield 50%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

n-Butyllithium (1.6 M in hexane, 48.3 mL) was added dropwise to a solution of N1,N1,N2,N2-tetramethylethane-1,2-diamine (8.08 g) and tert-butyl pyridin-2-ylcarbamate (5 g) in THF (dry) (50 mL) at −78° C. The mixture was stirred at 0° C. under N2 for 2 hr. Triisopropyl borate (16.95 g) was added to the mixture at −78° C. The mixture was stirred at 0° C. under N2 for 30 min. The mixture was quenched with sat. NH4Cl aq. at 0° C. and added with Et2O to give a yellow precipitate (11.68 g, wet). A mixture of potassium carbonate (438 mg), tetrakis(triphenylphosphine)palladium(0) (61.0 mg), 2,5-dibromopyridine (250 mg) and the precipitate (250 mg) in toluene (10 mL) and MeOH (5 mL) was stirred at 80° C. under N2 overnight. NH silica gel was added and the mixture was concentrated in vacuo. The residue was purified by column chromatography (NH silica gel, eluted with EtOAc in hexane) to give the title compound (132 mg) as a yellow solid.

Workup

  1. stirringThe mixture was stirred at 0° C. under N2 for 30 min
  2. customThe mixture was quenched with sat. NH4Cl aq. at 0° C.
  3. additionadded with Et2O
  4. customto give a yellow precipitate (11.68 g, wet)
  5. additionNH silica gel was added
  6. concentrationthe mixture was concentrated in vacuo
  7. customThe residue was purified by column chromatography (NH silica gel, eluted with EtOAc in hexane)

Sources & evidence

ORD record
ord-19483cd5324e4b5dab1f99c5c607d4a7
Source dataset
uspto-grants-2015_10
Patent number
US09150591B2

Reaction notes

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