Au2O3 as a Stable and Efficient Catalyst for the Selective Cycloisomerization of γ-Acetylenic Carboxylic Acids to γ-Alkylidene-γ-Butyrolactones

Patrick Yves Toullec; Emilie Genin; Sylvain Antoniotti; Jean-Pierre Genêt; Véronique Michelet

doi:10.1055/s-2008-1032108

LETTER

Au₂O₃ as a Stable and Efficient Catalyst for the Selective Cycloisomerization of γ-Acetylenic Carboxylic Acids to γ-Alkylidene-γ-Butyrolactones

Patrick Yves Toullec, Emilie Genin, Sylvain Antoniotti, Jean-Pierre Genêt, Véronique Michelet*
Laboratoire de Synthèse Sélective Organique et Produits Naturels, ENSCP, UMR 7573, 11 Rue P. et M. Curie, 72231 Paris Cedex 05, France
Fax: +33(1)44071062; e-Mail: veronique-michelet@enscp.fr;

Abstract

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Abstract

The high potential of commercially available Au₂O₃ as a catalyst in the cyclization of alkynes bearing carboxylic acids to the corresponding γ-alkylidene-γ-butyrolactones through a general, efficient and easy procedure is presented. The reaction shows a high degree of chemo-, regio-, and stereoselectivity. The 5-exo mode of cyclization and anti auration are a general trend for the Au₂O₃ catalyst.

Keywords

gold catalyst - cycloisomerization - γ-acetylenic carboxylic acids - atom economy - γ-alkylidene-γ-butyrolactones

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References

References and Notes

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General Procedure for the Cycloisomerization of γ-Acetylenic Acid 1
Substrate 1b (98 mg, 1 mmol) was placed in 5 mL Schlenk tube under argon and 1 mL of degassed MeCN was added. Gold(III) oxide (11.1 mg, 0,025 mmol) was added and the reaction mixture stirred at r.t. for 2 h. Filtration of the reaction mixture on a pad of 2 cm of silica using 15 mL of EtOAc and evaporation of the solvents allowed the isolation of product 2b as colorless oil in an analytically pure form (89 mg, 90% yield).

2-(Methoxycarbonyl)-2-(prop-2-ynyl)hex-5-ynoic Acid (1i)
Substrate 1i was prepared in a two-step procedure using malonic synthesis. Sodium hydride (1.1 equiv, 60 wt.% in mineral oil) was added portionwise at 0 °C to a solution of dimethyl propargylmalonate (1 equiv) in anhydrous DMF. The reaction was allowed to warm up to r.t. and but-3-ynyl trifluoromethylsulfonate ester (1.1 equiv) slowly added. The mixture was stirred at r.t. overnight, quenched upon addition of 10 mL of H₂O and extracted with Et₂O (3 × 20 mL). The combined organic layers were washed with brine (30 mL), dried over MgSO₄, and solvents evaporated under reduced pressure. Dimethyl 2-(but-3-ynyl)-2-(prop-2-ynyl)malonate was obtained as a colorless oil (18%) after purification by silica gel chromatography (cyclohexane-EtOAc, 90:10). Monosaponification was conducted following a reported procedure.¹⁴ A solution of KOH (1.2 equiv) in anhydrous MeOH (0.4 mol/L) was added to a cooled (0 °C) solution of substrate (1 equiv) in anhydrous MeOH (0.4 mol/L). The mixture was stirred at r.t. for 6 h. Solvent was removed under reduced pressure and the crude product redissolved in Et₂O. The organic layer was treated three times with sat. NaHCO₃, the aqueous phases collected, acidified to pH 1 with concd HCl, and then extracted with Et₂O. This organic layer was then dried over MgSO₄ and the solvents removed under reduced pressure to give 1i as a colorless oil (48% yield).
2-Methoxycarbonyl-2-[but-3′-ynyl]-4-methylene-butyrolactone (2i) ¹H NMR (300 MHz, CDCl₃): δ = 4.80-4.83 (m, 1 H), 4.39-4.41 (m, 1 H), 3.79 (s, 3 H), 3.39 (dt, J = 18.9, 2.0 Hz, 1 H), 2.98 (dt, J = 18.9, 2.0 Hz, 1 H), 2.05-2.40 (m, 4 H), 1.99 (t, J = 2.6 Hz, 1 H). ¹³C NMR (75.4 MHz, CDCl₃): δ = 171.9, 168.9, 152.3, 89.9, 82.1, 69.8, 54.6, 53.4, 35.3, 32.6, 14.3. MS (CI, NH₃): m/z (%) = 209 (8) [M + H]⁺, 226 (100) [M + NH₄]⁺, 244 (8) [M + NH₃ + NH₄]⁺. HRMS (CI-NH₃): m/z calcd for C₁₁H₁₃O₄: 209.0814; found: 209.0819.

2,2-Dimethylhept-4-ynoic Acid (1l) Methyl isobutyrate (1.07g, 10.5 mmol) was added dropwise at -78 °C to a solution of LDA solution in THF (15 mL, 0.7 mol/L, 10.5 mmol). The solution was stirred at -78 °C for 20 min then 1-bromobut-2-yne (1.47g, 10 mmol) slowly added dropwise. The reaction was stirred at -78 °C for 2 h then allowed to warm up to r.t. The reaction mixture was quenched with sat. aq NaHCO₃ solution and extracted with Et₂O. The combined organic layers were collected, washed with brine, dried over MgSO₄, and the solvents removed under reduced pressure. The crude oil was purified by flash chromatography [PE (30-60)-EtOAc, 95:5] to give methyl 2,2-dimethylhept-4-ynoate as a colorless oil (1.48 g, 88% yield). Saponification was conducted following a published procedure.² Methyl 2,2-dimethylhept-4-ynoate (1.01g, 6 mmol) was added to a solution of KOH (403 mg, 7.2 mmol) in MeOH and the reaction mixture was stirred at r.t. for 16 h. Solvent was removed under reduced pressure and the crude product dissolved in Et₂O. The organic layer was treated three times with sat. Na₂CO₃, the aqueous phases collected, acidified to pH 1 with concd HCl, and then extracted with Et₂O. This organic layer was then dried over MgSO₄ and the solvents removed under reduced pressure to give 1l as a colorless oil (590 mg, 64% yield). ¹H NMR (300 MHz, CDCl₃): δ = 2.41 (t, J = 2.4 Hz, 2 H), 2.16 (qt, J = 7.5, 2.4 Hz, 2 H), 1.28 (s, 3 H), 1.11 (t, J = 7.5 Hz, 1 H). ¹³C NMR (75.4 MHz, CDCl₃): δ = 183.2, 84.3, 75.5, 42.2, 29.7, 24.3, 14.2, 12.4. MS (CI, NH₃): m/z (%) = 155 (15) [M + H]⁺) 172 (100) [M + NH₄]⁺. HRMS (CI-NH₃): m/z calcd for C₉H₁₅O₂: 155.1072; found: 155.1075.
2,2-Dimethyl-4-propylydenebutyrolactone (2l) ¹H NMR (300 MHz, CDCl₃): δ = 4.60 (tt, J = 7.4, 1.7 Hz, 1 H), 2.61 (dt, J = 1.5, 1.5 Hz, 2 H), 2.16 (dtq, J = 7.5, 7.4, 1.4 Hz, 2 H), 1.29 (s, 6 H), 0.98 (t, J = 7.5 Hz, 3 H). ¹³C NMR (75.4 MHz, CDCl₃): δ = 180.4, 144.8, 107.2, 40.8, 40.0, 24.6, 18.5, 14.2. MS (CI, NH₃): m/z (%) 172 (20) [M + NH₄]⁺, 188 (100) [M + NH₄ + H₂O]⁺. HRMS (CI-NH₃): m/z calcd for C₉H₁₅O₂: 155.1072; found: 155.1071.