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DOI: 10.1055/s-2002-34870
Montmorillonite K10-Catalyzed Aza Diels-Alder Reaction of Danishefsky’s Diene with Aldimines, Generated in situ from Aliphatic Aldehydes and Amine, in Aqueous Media
Publikationsverlauf
Publikationsdatum:
21. Oktober 2002 (online)
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Abstract
The montmorillonite K10-catalyzed aza Diels-Alder reaction of Danishefsky’s diene with aldimines, generated in situ from aliphatic aldehydes and p-anisidine, proceeded smoothly in H2O or in aqueous CH3CN to afford 2-substituted 2,3-dihydro-4-pyridones in excellent yields.
Key words
Diels-Alder reactions - Danishefsky’s dienes - montmorillonite - water - Schiff bases
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Although we have reported the three-component aza Diels-Alder reaction of aldimine, derived from aliphatic aldehydes, with Danishefsky’s diene, [11] yields of the adducts are not excellent.
17General experimental procedure for conditions B (entry 5 of Table [3] ): To a solution of CH3CN (0.9 mL) and H2O (0.1 mL) were added p-anisidine (17.7 mg, 0.144 mmol), butanal (14.0 µL, 0.155 mmol) at -10 °C. After being stirred at the temperature for 10 min, Danishefsky’s diene (82.0 µL, 0.429 mmol) and montmorillonite K10 (75.4 mg) were added successively. After being stirred at the temperature another 1.5 h, catalysts were removed by filtration. The montmorillonite K10 was washed with a mixture of CH2Cl2-MeOH (4:1). The filtrate was dried over anhydrous Na2SO4, and concentrated to dryness. Purification of the crude mixture by preparative TLC (SiO2, hexane-ethyl acetate = 10: 1, v/v, containing 2% Et3N) gave propyl-substituted 2,3-dihydro-4-pyridone (34.6 mg, 0.141 mmol) in 89% yield.
18The reaction in water was run at 0 °C (bath temperature), while those in CH3CN-H2O and CH3CN were carried out at -10 °C.