Tributyltin Chloride → (3-Tributylstannyl-pyridin-4-yl)-carbamic acid tert-butyl ester

HRID 2183718Notes

Reaction equation

HRID 2183718 reaction equation
[C:1]([O:5][C:6](=[O:14])[NH:7][C:8]1[CH:13]=[CH:12][N:11]=[CH:10][CH:9]=1)([CH3:4])([CH3:3])[CH3:2].C([Li])(C)(C)C.[CH2:20]([Sn:24](Cl)([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:25][CH2:26][CH2:27][CH3:28])[CH2:21][CH2:22][CH3:23].[Cl-].[NH4+]>C1COCC1>[C:1]([O:5][C:6](=[O:14])[NH:7][C:8]1[CH:13]=[CH:12][N:11]=[CH:10][C:9]=1[Sn:24]([CH2:25][CH2:26][CH2:27][CH3:28])([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:20][CH2:21][CH2:22][CH3:23])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 4

HCID 15096Tributyltin ChlorideHCID 25517Ammonium ChlorideHCID 99902104-(Boc-amino)pyridineHCID 178418306HCID 178418306, compound

Product 1

HCID 69595531(3-Tributylstannyl-pyridin-4-yl)-carbamic acid tert-butyl esterYield 49%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

Pyridin-4-yl-carbamic acid tert-butyl ester (1.74 g, 8.95 mmol) (prepared as described in Venuti et al, J. Med. Chem. 1988, 31(11), 2136-45) dissolved in THF (150 mL) was cooled to −78° C. and a solution of 1.7M tert-butyllithium in hexanes (11.6 mL, 19.70 mmol) was added dropwise. After the addition, the stirring was continued for 1 h to −78° C. and the solution was then allowed to warm to −20° C. and stirred for an additional 3 h. The reaction was cooled again to −78° C. and tributyltin chloride (2.91 mL, 10.74 mmol) was added dropwise and the reaction was allowed to reach room temperature overnight. A saturated ammonium chloride solution was added and the product extracted with dichloromethane. The combined organics were dried over magnesium sulfate, the solvent was evaporated and residue purified by flash chromatography eluting with 20% ethyl acetate in hexanes to yield 2.12 g of (3-tributylstannyl-pyridin-4-yl)-carbamic acid tert-butyl ester.

Workup

  1. additionAfter the addition
  2. temperatureto warm to −20° C.
  3. temperatureThe reaction was cooled again to −78° C.
  4. waitto reach room temperature overnight
  5. extractionthe product extracted with dichloromethane
  6. dry with materialThe combined organics were dried over magnesium sulfate
  7. customthe solvent was evaporated
  8. customresidue purified by flash chromatography
  9. washeluting with 20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-0774844bd4dd44049d11d1395ef5e60c
Source dataset
uspto-grants-2005_05
Patent number
US06900220B2

Reaction notes

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