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Synlett 2009(14): 2346-2350  
DOI: 10.1055/s-0029-1217718
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient Organocatalytic Hetero-Diels-Alder Reactions of Activated Ketones under High Pressure for Direct Access to δ-Lactones [¹]

Kaori Moria, Jacques Maddalunob, Keiji Nakanoa, Yoshiyasu Ichikawaa, Hiyoshizo Kotsuki*a
a Laboratory of Natural Product Chemistry, Faculty of Science, Kochi University, Akebono-cho, Kochi 780-8520, Japan
Fax: +81(888)448359; e-Mail: kotsuki@kochi-u.ac.jp;
b IRCOF, CNRS UMR 6014 & FR 3038, Université de Rouen, 76821 Mont Saint-Aignan Cedex, France
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Publikationsverlauf

Received 20 May 2009
Publikationsdatum:
31. Juli 2009 (online)

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Abstract

A general and efficient protocol for the high-pressure-promoted hetero-Diels-Alder reactions of activated ketones has been developed. The reactions are successfully achieved by thiourea-derived organocatalysts, and the desired adducts, convenient precursors of δ-lactones, are obtained in good to high yields.

Key words

Hetero-Diels-Alder reaction - activated ketones - δ-lactones - thiourea catalyst - high pressure

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15

General Procedure A mixture of diene (2, 1.0 mmol) and ketone (3, 0.25 mmol) in the presence of 1a (0.1 mmol) in toluene or CH2Cl2 (ca. 2.5 mL) was placed in a Teflon reaction vessel, and the mixture was allowed to react at 1.0 GPa and r.t. for 10 h. After the pressure was released, the mixture was concentrated and purified by silica gel column chromatog-raphy (elution with hexane-Et2O) to afford the pure adduct 4.

18

Typically, treatment of 4a with excess Jones’ reagent in acetone (0 ˚C, 3 h) gave the corresponding dihydropyranone 5 in 60% yield: colorless needles (Scheme  [²] ); mp 104-105 ˚C (hexane-CH2Cl2). FTIR (KBr): ν = 1745, 1718 cm-¹. ¹H NMR (400 MHz, CDCl3): δ = 2.85 (1 H, dt, J = 18.2, 2.5 Hz), 3.49 (1 H, ddd, J = 18.2, 5.8, 1.0 Hz), 3.73 (3 H, s), 6.12 (1 H, ddd, J = 9.8, 2.5, 1.0 Hz), 6.91 (1 H, ddd, J = 9.8, 5.8, 2.5 Hz), 7.33-7.44 (3 H, m), 7.60-7.63 (2 H, m). ¹³C NMR (100 MHz, CDCl3): δ = 33.0, 53.4, 84.2, 121.8, 124.9 (2×), 128.7 (2×), 128.9, 137.1, 143.6, 162.2, 171.0. Anal. Calcd for C13H12O4: C, 67.23; H, 5.21. Found: C, 67.13; H, 5.35.

Scheme 2