Electrocatalytic Synthesis of 1,2-Dioxolanes from Tetrasubstituted Donor–Acceptor Cyclopropanes

Abstract

An electrochemical method for the synthesis of 3,3,5,5-tetrasubstituted 1,2-dioxolanes from donor–acceptor cyclopropanes with quaternary donor positions is described. This catalyst-free strategy delivers radical cations after C(sp³)–C(sp³) cleavage by direct anodic oxidation of the strained carbocycle. A broad scope with regard to the cyclopropanes employed in the reaction is presented. Additionally, we propose a plausible mechanism for the reaction.

Key words

donor–acceptor systems - cyclopropanes - dioxolanes - electrochemistry

• References and Notes

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• 17 Electrocatalytic Synthesis of 1,2-Dioxolanes: General Procedure In a 5 mL ElectraSyn vial, the appropriate cyclopropane 1 (200 μmol, 1.00 equiv) and TBABF₄ (0.02 M) were dissolved in HFIP (3.0 mL), and the solution was saturated with O₂ for 5 min. The solution was then electrolyzed at a glassy carbon anode and a glassy carbon cathode at a constant current of 1 mA. The vial was refilled with HFIP (1.5 mL) 5 min after the electrolysis was started. After 1 F/mol had been delivered, the mixture was concentrated in vacuo and the residue was purified by column chromatography (silica gel, pentane–EtOAc). Dimethyl 5-Methyl-5-phenyl-1,2-dioxolane-3,3-dicarboxylate (2a) Prepared by the general procedure and purified by column chromatography [silica gel, pentane–EtOAc (20:1 to 10:1)] to give a colorless solid; yield: 333.2 mg (40%, 1.19 mmol); mp 101 °C. IR (ATR): 2958, 2926, 1748, 1495, 1441, 1375, 1270, 1201, 1164, 1096 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 7.44–7.41 (m, 2 H), 7.37–7.33 (m, 2 H), 7.29–7.26 (m, 1 H), 3.87 (s, 3 H), 3.64 (s, 3 H), 3.56 (d, J = 12.7 Hz, 1 H), 3.36 (d, J = 12.7 Hz, 1 H), 1.67 (s, 3 H). ¹³C NMR (126 MHz, CDCl₃): δ = 167.7, 167.1, 142.7, 128.6 (2 C), 127.8, 125.1 (2 C), 88.5, 88.0, 54.3, 53.8, 53.5, 26.2. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₄H₁₆NaO₆: 303.0839; found: 303.0835.
• 18 CCDC 2284385 contains the supplementary crystallographic data for compound 2a. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures