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DOI: 10.1055/s-2004-834796
Ru-Catalyzed Enantioselective Dipolar Cycloadditions of Ethyl Diazopyruvate
Publikationsverlauf
Publikationsdatum:
20. Oktober 2004 (online)
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Abstract
The decomposition of ethyl diazopyruvate (1) with [RuCl2(pybox)] catalysts in the presence of enol ethers affords dihydrofurans derived from formal 1,3-cycloaddition. Enantioselectivities of up to 74% have been achieved.
Key words
asymmetric catalysis - cycloaddition - diazo compounds - carbenes - ruthenium
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18Sample Run. Cycloaddition of 1 to 2 in PhCH 3 . Ethyl 4,5-dihydro-3a H -furo[2,3- b ]furan-2-carboxylate ( 3): (S,S)-2,6-Bis(4-isopropyl-2-oxazolin-2-yl)pyridine (86 mg, 0.294 mmol) was added to a solution of [RuCl2(p-cymene)]2 (58 mg, 0.095 mmol) in CH2Cl2. The dark red mixture was stirred at r.t. for 1 h under argon atmosphere. The solvent was removed under reduced pressure. Dihydrofuran (1.4 mL) and a solution of ethyl diazopyruvate (100 mg, 0.950 mmol) in PhCH3 (3.0 mL) was added. The resulting suspension was stirred until complete consumption of starting material (thin layer chromatography). The mixture was concentrated, and the residue was purified by column chromatography on silica gel using EtOAc-pentane (60:40) as eluent afforded a pale yellow oil in 68% yield (104 mg, 0.620 mmol); [α]D 20 17 (c 1.12, CDCl3) for 74% ee. IR: 2983, 2281, 1737, 1633 cm-1. 1H NMR (300 MHz, CDCl3): d = 6.25 (d, J = 8.0 Hz, 1 H), 5.84 (d, J = 3.5 Hz 1 H), 4.32 (q, J = 9.3 Hz, 2 H), 4.11 (m, 1 H), 3.78 (m, 2 H), 2.13 (m, 1 H), 1.96 (m, 3 H). 13C NMR (75 MHz, CDCl3): δ = 159.7 (s), 148.8 (s), 111.7 (d), 110.5 (d), 67.1 (t), 61.4 (t), 47.6 (d), 31.2 (t), 14.2 (q). HRMS: m/z calcd for C9H12O4 +: 184.0738; found: 184.0718. Enantiomer separation: Supelco β-dex column (isothermal 140 °C) τ1: 43.9 min (87%), τ2: 45.7 min (13%).