Tributyltin Chloride → 7-Chloro-2-(tributylstannyl)thieno[3,2-b]pyridine

HRID 1898656Notes

Reaction equation

HRID 1898656 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[C:9](I)[S:10][C:3]=12.C([Mg]Cl)(C)C.[CH2:17]([Sn:21](Cl)([CH2:26][CH2:27][CH2:28][CH3:29])[CH2:22][CH2:23][CH2:24][CH3:25])[CH2:18][CH2:19][CH3:20]>C1COCC1>[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[CH:8]=[C:9]([Sn:21]([CH2:22][CH2:23][CH2:24][CH3:25])([CH2:26][CH2:27][CH2:28][CH3:29])[CH2:17][CH2:18][CH2:19][CH3:20])[S:10][C:3]=12

Participants

5

Reactant 3

HCID 15096Tributyltin ChlorideHCID 177504007-Chloro-2-iodothieno(3,2-b)pyridineHCID 178418918HCID 178418918, compound

Product 1

HCID 575166587-Chloro-2-(tributylstannyl)thieno[3,2-b]pyridineYield 52%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

In a round bottom flask, 7-chloro-2-iodothieno[3,2-b]pyridine (200 mg, 0.68 mmol) was suspended in THF (6 mL). The reaction mixture was cooled with a NaCl-ice bath (−12 to −8° C. internal temp) and isopropylmagnesium chloride (2.0 M in THF, 0.406 mL, 0.812 mmol) was added dropwise. The reaction mixture was stirred for 1 h at the same temperature, and then tributyltin chloride (0.29 mL, 1.08 mmol) was slowly added. The reaction mixture was allowed to warm to room temperature over ˜1 h then quenched with an aqueous solution of NH4Cl (20 mL) and extracted with EtOAc (30 mL). The organic layer was dried over Na2SO4 and evaporated to dryness. The crude residue was purified by column chromatography (SiO2-11 g-Et3N 2%, hexanes 100% 5 min, to hexanes:EtOAc, 9:1 in 15 min) to isolate 162 mg (52%) of 7-chloro-2-tributylstannanyl-thieno[3,2-b]pyridine as a colorless oil.

Workup

  1. additionwas added dropwise
  2. customthen quenched with an aqueous solution of NH4Cl (20 mL)
  3. extractionextracted with EtOAc (30 mL)
  4. dry with materialThe organic layer was dried over Na2SO4
  5. customevaporated to dryness
  6. customThe crude residue was purified by column chromatography (SiO2-11 g-Et3N 2%, hexanes 100% 5 min, to hexanes:EtOAc, 9:1 in 15 min)

Sources & evidence

ORD record
ord-007c71e96a6841aa80eb550506ae553f
Source dataset
uspto-grants-2013_08
Patent number
US08518945B2

Reaction notes

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