Tributylstannane → HCID 19843884, compound

HRID 2352147Notes

Reaction equation

HRID 2352147 reaction equation
[C:1]([OH:7])(=[O:6])[CH2:2][CH2:3][C:4]#[CH:5].[CH3:8][CH2:9][CH2:10][CH2:11][SnH:12]([CH2:17][CH2:18][CH2:19][CH3:20])[CH2:13][CH2:14][CH2:15][CH3:16].B(CC)(CC)CC.[F:28][C:29]1[C:34]([F:35])=[CH:33][C:32]([F:36])=[C:31]([F:37])[C:30]=1O.C1(N=C=NC2CCCCC2)CCCCC1>C1(C)C=CC=CC=1.C1COCC1>[CH2:13]([Sn:12]([CH2:11][CH2:10][CH2:9][CH3:8])([CH2:17][CH2:18][CH2:19][CH3:20])[C:4](=[CH2:5])[CH2:3][CH2:2][C:1]([O:7][C:30]1[C:29]([F:28])=[C:34]([F:35])[CH:33]=[C:32]([F:36])[C:31]=1[F:37])=[O:6])[CH2:14][CH2:15][CH3:16]

Participants

8

Reactant 5

HCID 5948TributylstannaneHCID 7357TriethylboraneHCID 10868DicyclohexylcarbodiimideHCID 224644-Pentynoic acidHCID 698582,3,5,6-Tetrafluorophenol

Product 1

HCID 19843884HCID 19843884, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of 4-pentynoic acid (308 mg, 3.1 mmol) in toluene (7.0 mL) under N2 was added Bu3SnH (1.7 mL, 6.3 mmol) followed by Et3B (0.30 mL, 1.0 M solution ion hexanes, 0.30 mmol). The resulting solution was stirred at room temperature for 13/4 hours after which the solvent was evaporated under reduced pressure. The resulting oil was dissolved in EtOAc and washed with saturated NaCl. The EtOAc layer was dried over MgSO4, filtered and concentrated under reduced pressure to afford 2.0 gr of crude product. To a solution of the crude product in anhydrous THF (15 mL) was added a solution 2,3,5,6-tetrafluorophenol (554 mg, 3.4 mmol) in THF (1.0 mL) followed by a solution of dicyclohexylcarbodiimide (652 mg, 2.3 mmol) in THF (1.0 mL). The resulting solution was stirred at room temperature overnight during which time a white precipitate formed. The THF was evaporated under reduced pressure and the residue was suspended in CH3CN. The insoluble precipitate was filtered off and the filtrate was purified via flash chromatography (silica gel, 25 mm×90 mm, 5% EtOAc/hexanes) to afford 833 mg (50%) of 2,3,5,6-tetrafluorophenyl 4-(tri-n-butylstannyl)-4-pentenoate as a mixture of isomers. 1H NMR (200 MHz, CDCl3) S 6.90 (m, 1H), 6.20 (m, 2H), 2.78 (bq, 2H, J=7 Hz), 2.60 (m, 2H), 1.65-1.20 (m, 18H), 1.90 (t, 9H, J=9 Hz); 13CNMR (50.3Hz, CDCl3) S 169.75, 145.95, 145.80, 132.14, 130.77, 106.70 (t, J=23 Hz). 103.63 (t, J=23 Hz), 34.04, 33,13, 32.62, 32,23, 29.32, 27.63, 13.96, 10.53, 9.71.

Workup

  1. customwas evaporated under reduced pressure
  2. dissolutionThe resulting oil was dissolved in EtOAc
  3. washwashed with saturated NaCl
  4. dry with materialThe EtOAc layer was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customto afford 2.0 gr of crude product
  8. stirringThe resulting solution was stirred at room temperature overnight during which time a white precipitate
  9. customformed
  10. customThe THF was evaporated under reduced pressure
  11. filtrationThe insoluble precipitate was filtered off
  12. customthe filtrate was purified via flash chromatography (silica gel, 25 mm×90 mm, 5% EtOAc/hexanes)

Sources & evidence

ORD record
ord-e6547375fb5149c6abfba8cda06675f0
Source dataset
uspto-grants-1989_10
Patent number
US04876081

Reaction notes

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