α,β-Unsaturated δ-Valerolactones through RCM–Isomerization Sequence

Bernd Schmidt; Oliver Kunz

doi:10.1055/s-0031-1290488

Synlett, Table of Contents

Synlett 2012; 23(6): 851-854
DOI: 10.1055/s-0031-1290488

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α,β-Unsaturated δ-Valerolactones through RCM–Isomerization Sequence

Bernd Schmidt*

Universität Potsdam, Institut für Chemie (Organische Synthesechemie), Karl-Liebknecht-Straße 24-25, 14476 Potsdam-Golm, Germany, Fax: +49(331)9775059 Email: bernd.schmidt@uni-potsdam.de

,

Oliver Kunz

Universität Potsdam, Institut für Chemie (Organische Synthesechemie), Karl-Liebknecht-Straße 24-25, 14476 Potsdam-Golm, Germany, Fax: +49(331)9775059 Email: bernd.schmidt@uni-potsdam.de

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Abstract

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Abstract

α,β-Unsaturated δ-lactones are accessible via a sequential ring-closing metathesis (RCM) double-bond migration reaction starting from butenoates of allyl alcohols. This approach proceeds efficiently with lower catalyst loadings and higher initial substrate concentrations compared to the alternative RCM of acrylates derived from homoallylic alcohols.

Key words

ruthenium - lactones - tandem reactions - metathesis - esters

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References

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46 Representative Example: Synthesis of 1iA solution of 5i (200 mg, 0.7 mmol) in toluene (7.0 mL) was preheated to 80 °C, and catalyst B (6.0 mg, 1.0 mol%) was added. After the starting material was fully consumed (TLC, approx. 30 min), Et₃SiH (22 μL, 0.14 mmol) was added, and the solution was heated to reflux for 1 h. All volatiles were evaporated, and the residue was purified by chromatography on silica (eluent: hexane–MTBE = 5:1) to give α-pyrone 1i (152 mg, 85%) as a colorless oil. [α]²⁴ _D +117.3 (c 0.56, CH₂Cl₂). ¹H NMR (300 MHz, CDCl₃): δ = 6.90 (ddd, J = 9.6, 5.8, 2.7 Hz, 1 H), 6.00 (dm, J = 9.7 Hz, 1 H), 4.19 (dt, J = 11.1, 5.0 Hz, 1 H), 4.00 (qm, J = 6.3 Hz, 1 H), 2.57–2.35 (2 H), 1.22 (d, J = 6.3 Hz, 3 H), 0.88 (9 H), 0.09 (3 H), 0.08 (3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 168.5 (0), 145.1 (1), 121.1 (0), 81.7 (1), 69.3 (1), 25.8 (3), 24.3 (2), 20.2 (3), 18.0 (0), –4.5 (3), –4.7 (3). IR (neat): ν = 2957 (m), 2931 (m), 2897 (w), 1723 (s), 1383 (m), 1249 (s), 1075 (s). ESI-MS: m/z = 239 (5), 257 (35), 279 (100) [M + Na]⁺. ESI-HRMS: m/z calcd for C₁₃H₂₄NaO₃Si⁺ [M + Na]⁺: 279.1392; found: 279.1375. Anal. Calcd (%) for C₁₃H₂₄O₃Si (256.41): C, 60.9, H, 9.4. Found: C, 60.7; H, 9.6

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