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Reaction mechanism and chemoselectivity of gold(I)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles to yield substituted furans

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Abstract

The mechanisms of gold(I)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles have been investigated using density functional theory calculations at the B3LYP/6-31G (d, p) level of theory. A polarizable continuum model (PCM) has been established in order to evaluate the effects of solvents on the reactions. The results of the calculations indicate that the first step of the catalytic cycle is the cyclization of the carbonyl oxygen onto the triple bond which forms a new and stable resonance structure of an oxonium ion and a carbocation intermediate. The subsequent ring expansion step results in the formation of the final product and regeneration of the catalyst. Furthermore, the regioselectivity and effect of substituents has been discussed, including an analysis of energy, bond length, and natural bond orbital (NBO) charge distributions in the rate-determining step. Our computational results are consistent with earlier experimental observations.

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Authors and Affiliations

  1. Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Gansu, 730070, China

    YunFeng Yan, ZhiYuan Geng, YongCheng Wang & ShaoLi Liu

  2. College of Chemistry and Chemical Engineering, Lanzhou University, Gansu, 730000, China

    Ran Fang

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  1. YunFeng Yan
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Correspondence to ZhiYuan Geng.

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Yan, Y., Fang, R., Geng, Z. et al. Reaction mechanism and chemoselectivity of gold(I)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles to yield substituted furans. Sci. China Chem. 55, 1413–1420 (2012). https://doi.org/10.1007/s11426-012-4573-2

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