N,N,N',N'-Tetramethylethylenediamine → HCID 66748454, compound

HRID 1405733Notes

Reaction equation

HRID 1405733 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-].[Na+].[Na+].I[C:48]1[CH:53]=[CH:52][C:51]([N:54]2[CH2:58][CH2:57][CH2:56][CH2:55]2)=[CH:50][CH:49]=1>C1COCC1.COCCOC.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:54]1([C:51]2[CH:52]=[CH:53][C:48]([C:16]3[CH:15]([NH2:20])[NH:14][CH:19]=[CH:18][CH:17]=3)=[CH:49][CH:50]=2)[CH2:58][CH2:57][CH2:56][CH2:55]1

Participants

11

Reactant 6

HCID 8037N,N,N',N'-TetramethylethylenediamineHCID 10340Sodium CarbonateHCID 21531Triisopropyl borateHCID 112063492-(Boc-amino)pyridineHCID 112773071-(4-iodophenyl)pyrrolidineHCID 178418339Butyllithium

Product 1

HCID 66748454HCID 66748454, compoundYield 9.7%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
0 °C

Procedure

n-Butyllithium (1.6 M in hexane, 48.3 mL) was added dropwise to a solution of N,N,N′,N′-tetramethylethane-1,2-diamine (8.08 g) and tert-butyl pyridin-2-ylcarbamate (5.00 g) in THF (dry) (50 mL) at −78° C. The mixture was stirred at 0° C. under N2 for 2 hr. Triisopropyl borate (17.0 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 (11.7 g, wet). A mixture of the precipitate (349 mg), sodium carbonate (155 mg), tetrakis(triphenylphosphine)palladium(0) (42.3 mg) and 1-(4-iodophenyl)pyrrolidine (200 mg) in DME (25 mL) and water (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 (17.1 mg) as a white solid.

Workup

  1. stirringThe mixture was stirred at 0° C. under N2 for 30 min
  2. customThe mixture was quenched
  3. additionNH4Cl aq. at 0° C. and added with Et2O
  4. customto give a yellow precipitate (11.7 g, wet)
  5. stirringwas stirred at 80° C. under N2 overnight
  6. additionNH silica gel was added
  7. concentrationthe mixture was concentrated in vacuo
  8. customThe residue was purified by column chromatography (NH silica gel, eluted with EtOAc in hexane)

Sources & evidence

ORD record
ord-411bc09ec9f74b67be75aaa3780e0522
Source dataset
uspto-grants-2014_12
Patent number
US08916551B2

Reaction notes

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