Copper(I)-Catalyzed Synthesis of Polysubstituted Furans from Alkynoates and 1,3-Dicarbonyl Compounds in the Presence of Oxygen

Abstract

A novel and straightforward synthesis of polysubstituted furans was achieved easily from the oxidative cyclization of 1,3-dicarbonyl compound and alkynoate catalyzed by CuI in the presence of O_2.

polysubstituted furans - oxidant - copper catalysis - oxygen.

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11

General Procedure for the Preparation of Dimethyl But-2-yndioate and 1,3-Diphenyl-1,3-propanedione (3aa)
An oven-dried Schlenk tube was charged with CuI (9.5 mg, 0.05 mmol), 1a (0.50 mmol), and 2a (0.50 mmol). The Schlenk tube was sealed and then evacuated and backfilled with oxygen (3 cycles). Then DMF (2 mL) was added to the reaction system. The reaction was stirred at 110 ˚C under O₂ (1 atm) for 4 h. After cooling to r.t., the solvent diluted with Et₂O (10 mL) and washed with brine (5 mL) and dried over anhyd Na₂SO₄. After the solvent was evaporated in vacuo, the residues were purified by column chromatography, eluting with PE-EtOAc (10:1) to afford pure 3aa.
Dimethyl 4-Benzoyl-5-phenylfuran-2, 3-dicarboxylate (3aa) Yellow viscous oil. ^¹H NMR (400 MHz CDCl₃): δ = 3.61 (s, 3 H), 3.96 (s, 3 H), 7.29-7.39 (m, 5 H), 7.50-7.54 (m, 1 H), 7.61-7.63 (m, 2 H), 7.79-7.81 (m, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 52.4, 52.5, 121.5, 126.2, 127.4, 127.6, 128.5, 128.6, 129.3, 130.2, 133.6, 136.7, 141.1, 155.3, 157.7, 161.9, 190.0. IR (neat): 694, 772, 899, 1080, 1167, 1235, 1443, 1666, 1730, 2953, 3004, 3062 cm^-¹. HRMS (EI): m/z calcd for C₂₁H₁₆O₆ [M + H]⁺: 365.1020; found: 365.1029.
The ^¹H NMR, ^¹³C NMR, IR, and HRMS data of 3aa-bb can be found in the Supporting Information.