A new type of dendritic NOBIN derived Schiff base ligands has been synthesized and applied to titanium catalyzed hetero-Diels-Alder reaction of Danishelfsky's diene and aldehydes, affording the corresponding 2-substituted 2,3-dihydro-4H-pyran-4-one in good yields and moderate enantioselectivities (up to 59.2% ee). It was found that the size of dendron attached to the tri-dentated ligands has slight impact on the enantioselectivity of the reaction and the second generation of dendritic ligand exhibited the best enantioselectivity.

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6 A typical procedure for HDA reaction: To a 10-mL flame dried Schlenck tube was added activated powdered 4 Å (50 mg), (S)-dendritic Schiff Base (0.05 mmol) ligand and naproxen (0.0125 mmol) under argon atmosphere. Dried toluene (1 mL) and Ti(Oⁱ Pr)₄ in dichloromethane (0.5 mol/L, 50 μL, 0.025 mmol) were subsequently injected, respectively. The resulting red solution was heated to 50 °C for 2 h and then cooled to room temperature. Aldehyde (0.25 mmol) and Danishelfsky's diene (80 μL, 0.4 mmol) were added sequentially. The mixture was stirred at room temperature for 48 h before quenched with 10 drops of TFA. After stirring for additional 5 min, the mixture was neutralized with saturated NaHCO₃ (about 3 mL) and extracted with ethyl ether (3 × 6 mL). The combined organic layers were dried over anhydrous Na₂SO₄ and concentrated to dryness. The residue was purified by flash chromatography to give the cycloadduct.
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Volume21, Issue7

July 2003

Pages 727-730

Synthesis of Dendritic Schiff Base Ligands for Titanium Catalyzed Enantioselective HDA Reaction of Danishelfsky's Diene with Aldehydes^†

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Synthesis of Dendritic Schiff Base Ligands for Titanium Catalyzed Enantioselective HDA Reaction of Danishelfsky's Diene with Aldehydes†

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Synthesis of Dendritic Schiff Base Ligands for Titanium Catalyzed Enantioselective HDA Reaction of Danishelfsky's Diene with Aldehydes^†