Lipase-Induced Oxidative Furan Rearrangements

Published as part of the Special Section 9^th EuCheMS Organic Division Young Investigator Workshop

Abstract

Lipase B from Candida antarctica catalyzes the oxidative ring expansion of furfuryl alcohols using aqueous hydrogen peroxide to yield functionalized pyranones under mild conditions. The method further allows for the preparation of corresponding piperidinone derivatives by enzymatic rearrangement of N-protected furfurylamines.

Key words

Achmatowicz - ring expansion - furan - pyranone - synthetic methodology - heterocyclic chemistry

• References and Notes

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• 16 Representative Experimental Procedure The appropriate furfuryl alcohol (5 mmol) was dissolved in EtOAc (50 mL), and CAL-B (105 mg, 1.5 kU) and aq. H₂O₂ (50 % 858 μL, 15 mmol) were added. The reaction mixture was placed on an orbital shaker at 40 °C (200 rpm). After 24 h, phosphate buffer (15 mL, 100 mM, pH 7.0) and catalase (5 μL) were added, and the mixture was shaken for further 15 min. The organic phase was separated, and the aqueous phase was extracted with EtOAc (2 × 20 mL). The combined organic layers were dried over Na₂SO₄ and volatiles were removed under reduced pressure. The crude product was purified by flash column chromatography (hexane/EtOAc). 6-Hydroxy-2,2-dimethyl-2H-pyran-3(6H)-one (2h) Purified by column chromatography (SiO₂, n-hexane/EtOAc 3:1 to 2:1) to give a colorless liquid (547 mg, 3.85 mmol, 77%). R_f = 0.33 (n-hexane/EtOAc, 2:1). ¹H NMR (400 MHz, CDCl₃): δ = 6.87 (dd, ³ J = 10.3 Hz, ³ J = 2.2 Hz, 1 H), 6.07 (dd, ³ J = 10.3 Hz, ⁴ J = 1.3 Hz, 1 H), 5.70–5.68 (m, 1 H), 3.38 (br s, 1 H), 1.49 (s, 3 H), 1.39 (s, 3 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 198.9, 145.7, 126.6, 88.0, 79.5, 26.6, 23.9 ppm. FT-IR (ATR): ν = 3402 (br), 2982 (w), 1681 (s), 1380 (m), 1293 (m), 1238 (m), 1084 (m), 1036 (s), 924 (m) cm^–1.
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