Cobalt Porphyrin Catalyzed [3+2] Cycloaddition of Cyclopropanes and Carbonyl Compounds

Abstract

A cobalt porphyrin efficiently catalyzed the formal [3+2] cycloaddition of alkyl-/aryl-substituted cyclopropanes and carbonyl compounds such as aldehydes and ketones to afford the corresponding substituted tetrahydrofurans. The use of the cobalt porphyrin complex as a Lewis acid to catalyze the reaction via the electrophilic activation of cyclopropanes was demonstrated. The high functional-group tolerance and robustness of the catalyst were also demonstrated. Further, the potential utility of the catalyst was demonstrated by performing the cycloaddition of cyclic ketones and cyclopropanes to afford spiro tetrahydrofurans.

Key words

aldehydes - catalysis - cycloaddition - furans - ketones

• References and Notes


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• 12 The [3+2] cycloaddition afforded tetrahydrofuran 3da (Table 2, entry 4) and 3ac (Table 3, entry 3) with low diasteroselectivity. These reactions proceed in high diasteroselectivity at initial stage, however, epimerization occurs upon completion of the reaction probably because electron-donating methoxy group facilitate the ring opening by stabilizing benzylic cation intermediate. For epimerization of the tetrahydrofurans with Lewis acid, see ref. 6e.
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• 14 General Procedure for the [3+2] Cycloaddition The reaction was performed in a 15 mL sealed tube equipped with a Teflon-coated magnetic stirrer bar. An aldehyde 2 (0.15 mmol) was added to a solution of cyclopropane 1 (0.1 mmol) and [Co(TPP)]TFPB (3.1 mg, 4 μmol) in DCE (1 mL) in a dry box. The sealed tube was taken outside the dry box and heated at 55 °C for the indicated time under argon atmosphere. The resulting reaction mixture was cooled to ambient temperature and filtered through a silica gel pad, concentrated in vacuo. The residue was purified by flash silica gel column chromatography (20 g, 2 × 15 cm; hexane–EtOAc, 5:1) to give the products 3.