Decarboxylation of Paraconic Acids by a Silver(I) Nitrate/Persulfate Combination: An Entry to β-Nitro- and β-Hydroxy γ-Butyrolactones

Abstract

Decarboxylative transformations of paraconic acids, a class of γ-butyrolactones containing a carboxylic acid group at the β-position as their characteristic functionality, by using a combination of AgNO₃/K₂S₂O₈ were investigated. The dual function of AgNO₃ as an initiator of the decarboxylation process and as a source of nitrogen dioxide radicals that react with aliphatic carboxylic substrates is reported for the first time. Starting from paraconic acids, β-nitro- and β-hydroxy γ-butyrolactones were obtained in good combined yields (41–85%) with moderate selectivity in a one-pot operation. The reactions were completed within an acceptable reaction time (two hours) under mild conditions that were tolerated by the γ-butyrolactone core. This study provides a direct and site-specific entry to β-nitro- and β-hydroxy γ-butyrolactones, which are important precursors in organic transformations.

Key words

decarboxylation - nitration - alkanoic acids - butyrolactones - nitroalkanes - paraconic acids

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• 16 5,5-Diethyl-4-nitrodihydrofuran-2(3H)-one (2a) and 5,5-Diethyl-4-hydroxydihydrofuran-2(3H)-one (3a): Typical Procedure To a mixture of 1a (1 mmol), AgNO₃ (3 equiv), and K₂S₂O₈ (1.25 equiv) was added anhyd MeCN (0.1 M), and the resulting suspension was stirred at the reflux for 2 h. The mixture was then cooled to r.t. and extracted with EtOAc (3 × 20 mL). The combined organic layer was washed with a sat. aq NaHCO₃ (20 mL) and brine, then dried (Na₂SO₄) and concentrated under reduced pressure. The residue was purified by flash column chromatography [silica gel, acetone–hexanes (1:4)] to give 2a as a pale-yellow oil [yield: 71.8 mg (38%)] and 3a as a pale-yellow oil [yield: 46.8 mg (30%)]. 2a R_f = 0.41 (acetone–hexanes, 1:4). IR (ATR): 1776, 1555, 1202, 1115, 961 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 5.06 (app. dd of ABX, J _BX = 3.0, J _AX = 7.6 Hz, 1 H, CH), 3.20 (ABq of ABX, J _BX = 3.0, J _AB = 18.8 Hz, 1 H, CHH), 2.99 (ABq of ABX, J _AX = 7.6, J _AB = 18.8 Hz, 1 H, CHH), 1.88–1.76 (m, 1 H, CHH), 1.76–1.55 (m, 3 H, CHH and CH ₂), 0.96 (t, J = 7.6 Hz, 3 H, CH ₃), 0.95 (t, J = 7.4 Hz, 3 H, CH ₃). ¹³C NMR (100 MHz, CDCl₃): δ = 171.3 (C), 89.3 (CH), 86.3 (C), 33.8 (CH₂), 28.8 (CH₂), 25.1 (CH₂), 7.7 (CH₃), 7.6 (CH₃). ¹⁵N NMR (60.8 MHz, CDCl₃): δ = 383.0–382.7. MS: m/z (%) = 188 (65) [M + H]⁺, 178 (46), 111 (20), 57 (100). HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₈H₁₃NNaO₄: 210.0737; found: 210.0739. 3a R_f = 0.22 (acetone–hexanes, 1:4). IR (ATR): 3410, 1742, 1275, 1114, 1079, 953 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 4.23 (app. dd of ABX, J _BX = 3.1, J _AX = 6.7 Hz, 1 H, CH), 2.88 (ABq of ABX, J _AX = 6.7, J _AB = 18.4 Hz, 1 H, CHH), 2.46 (ABq of ABX, J _BX = 3.1, J _AB = 18.4 Hz, 1 H, CHH), 2.15 (br s, 1 H, OH), 1.88–1.68 (m, 2 H, CH₂), 1.67–1.48 (m, 2 H, CH₂), 0.92 (t, J = 6.6 Hz, 3 H, CH₃), 0.88 (t, J = 6.6 Hz, 3 H, CH₃). ¹³C NMR (100 MHz, CDCl₃): δ = 175.3 (C), 92.6 (C), 71.8 (CH), 38.7 (CH₂), 28.0 (CH₂), 23.3 (CH₂), 7.8 (CH₃), 7.7 (CH₃). MS: m/z (%) = 159 (38) [M + H]⁺, 141 (100), 111 (34), 83 (50), 69 (17), 55 (41). HRMS (ESI-TOF): m/z [M + Na]⁺ calcd for C₈H₁₄NaO₃: 181.0834; found: 181.0837.