Carboxylative Cyclization of Propargylic Amines with Carbon Dioxide­ Catalyzed by Poly(amidoamine)-Dendrimer-Encapsulated Gold Nanoparticles

Abstract

We prepared gold nanoparticles encapsulated in poly(amidoamine) (PAMAM) dendrimers as templating agents. The resulting gold nanoparticles were used as catalysts for the carboxylative cyclization of propargylic amines with carbon dioxide to afford the corresponding 1,3-oxazolidin-2-ones in yields of up to 99%.

Key words

oxazolidinones - propargylic amines - carbon dioxide - gold catalysis - nanoparticles

• References and Notes

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For previously reported transformations catalyzed by the PAMAM-dendrimer-encapsulated gold nanoparticles, see:
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• 15 2: HAuCl₄/PAMAM = 20:1 (mol/mol), C/[Au] = 50:1 (w/w). A histogram showing the particle-size distribution of the gold nanoparticles 2 is given in the Supporting Information.
• 16 [Au]: weight of gold in hydrogen tetrachloroaurate(III).
• 17 In all cases in which 2 was prepared without hydrogen tetrachloroaurate(III) and/or PAMAM 1, the carboxylative cyclization of 3a with CO₂ did not proceed.
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• 19 1,3-Oxazolidin-2-ones 4a–e : General ProcedureA reaction vessel was charged with 10% methanolic solution of the fourth-generation PAMAM 1 (21 mg, 0.15 μmol) under argon. The MeOH was removed in vacuo, and 1 was redissolved in H₂O (2.1 mL). A 0.005 M aqueous solution of HAuCl₄ (0.6 mL) was slowly added to the aqueous solution of 1 with stirring. The mixture was stirred for 1 h, then a 0.1 M solution of NaBH₄ in 0.3 M aq NaOH (0.3 mL) was added dropwise with vigorous stirring to reduce the AuCl₄ ^– to Au nanoparticles. Immediately after the addition of the NaBH₄, mesoporous carbon powder (30 mg) was added, and the reaction mixture was vigorously stirred for 30 min to give the carbon-supported PAMAM-encapsulated gold nanoparticles 2 as an aqueous dispersion (3 mL in total), to which toluene (1.5 mL) was added with stirring. The atmosphere in the reaction vessel was then changed from argon to CO₂ and the mixture was heated at 40 °C. The appropriate propargylic amine 3 (0.3 mmol for Table 4, entries 1 and 2; 0.15 mmol for entries 3–6) was then added, and the mixture was vigorously stirred at 40 ºC under CO₂ at atmospheric pressure for the appropriate time. Catalyst 2 was separated by filtration under a vacuum and washed with CH₂Cl₂. The filtrate was collected and extracted with CH₂Cl₂ (×4). The combined organic layer was dried (Na₂SO₄) and filtered, and the yield of the1,3-oxazolidin-2-one 4 was determined by integration of its ¹H NMR absorption with reference to an internal standard [2-(benzyloxy)naphthalene]. 4a, 4b, and 4d were isolated by removal of the CH₂Cl₂ under reduced pressure and purified by column chromatography (silica gel, hexane–AcOEt).3-Benzyl-5-methylidene-1,3-oxazolidin-2-one (4a)yield: 57.4 mg (99%). ¹H NMR (400 MHz, CDCl₃): δ = 7.40–7.30 (m, 3 H), 7.30–7.25 (m, 2 H), 4.74 (td, J = 2.6, 3.1 Hz, 1 H), 4.47 (s, 2 H), 4.24 (td, J = 2.2, 3.1 Hz, 1 H), 4.02 (t, J = 2.4 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 155.6, 149.0, 135.0, 129.0, 128.25, 128.17, 86.7, 47.8, 47.2.
• 20 In Figure 3, it is assumed that the nucleophilic ring closure from 6 to 4 is probably retarded when an electron-donating methyl group is present at R¹.