Tributyltin Chloride → HCID 86713378, compound

HRID 928088Notes

Reaction equation

HRID 928088 reaction equation
C([Li])CCC.[C:6]([C@@H:8]1[CH2:12][CH2:11][CH2:10][N:9]1[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])#[CH:7].[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].C(=O)(O)[O-].[Na+]>C1COCC1>[CH2:29]([Sn:24]([CH2:20][CH2:21][CH2:22][CH3:23])([CH2:25][CH2:26][CH2:27][CH3:28])[C:7]#[C:6][C@@H:8]1[CH2:12][CH2:11][CH2:10][N:9]1[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:30][CH2:31][CH3:32]

Participants

6

Reactant 4

HCID 15096Tributyltin ChlorideHCID 516892Sodium BicarbonateHCID 11030701(S)-N-Boc-2-ethynylpyrrolidineHCID 178418339Butyllithium

Product 1

HCID 86713378HCID 86713378, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

n-Butyl lithium (2.5M solution in hexanes. 11 mL) was added dropwise to a cooled solution of tert-butyl (S)-2-ethynylpyrrolidine-1-carboxylate (prepared according A Paul et al, Tetrahedron, 2006, 62, 8919, 4.49 g) in dry THF (230 ml) under an atmosphere of nitrogen while maintaining the temperature below −65° C. When the addition was completed, the mixture was stirred at −78° C. for 15 minutes then allowed to warm to 0° C. and stirred for 2.5 hours. Tributyl tin chloride (7.7 mL) was added dropwise over five minutes and the mixture was stirred at room temperature for 1.5 hours. The mixture was cooled to 0° C. and saturated sodium bicarbonate was added while maintaining the temperature below 15° C. The layers were separated and the aqueous layer was extracted with ethyl acetate, washed with saturated sodium bicarbonate, water, dried (MgSO4) and filtered. The filtrate was evaporated to dryness and the residue was purified by chromatography on silica, eluting with a mixture of pentane and ethyl acetate with a gradient of 0-7.5% to give tert-butyl (S)-2-tributylstannanylethynylpyrrolidine-1-carboxylate (0.39 g) as an oil.

Workup

  1. customprepared
  2. temperaturewhile maintaining the temperature below −65° C
  3. additionWhen the addition
  4. temperatureto warm to 0° C.
  5. stirringstirred for 2.5 hours
  6. stirringthe mixture was stirred at room temperature for 1.5 hours
  7. temperatureThe mixture was cooled to 0° C.
  8. temperaturewhile maintaining the temperature below 15° C
  9. customThe layers were separated
  10. extractionthe aqueous layer was extracted with ethyl acetate
  11. washwashed with saturated sodium bicarbonate, water
  12. dry with materialdried (MgSO4)
  13. filtrationfiltered
  14. customThe filtrate was evaporated to dryness
  15. customthe residue was purified by chromatography on silica
  16. washeluting with a mixture of pentane and ethyl acetate with a gradient of 0-7.5%

Sources & evidence

ORD record
ord-94178be8a28249778981468cfddc9b44
Source dataset
uspto-grants-2016_03
Patent number
US09290472B2

Reaction notes

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