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<p>The precise manipulation of unfunctionalized hydrocarbons remains a fundamental challenge for chemical synthesis and catalysis. Stereodifferentiation in strained alkanes is particularly difficult to accomplish because a catalyst has to distinguish various highly exergonic chemo- and stereoselective strain-release channels. Here we disclose an organocatalytic asymmetric hydroalkoxylation of bicyclobutanes with alcohols to efficiently access tertiary cyclopropylcarbinyl ethers with high enantioselectivity (e.r. up to 98:2). Enantiocontrol is accomplished through chiral recognition between the confined iminoimidodiphosphoric acid catalyst and the substrate, mediated by non-covalent interactions between a Lewis basic binding site of the confined anion and the polarized C–H bond of the cyclopropylcarbinyl ion intermediate. Our work establishes bicyclobutane activation by harnessing strain-release energetics while maintaining precise stereo- and regiocontrol through structural confinement.</p><p></p>

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Catalytic asymmetric activation of bicyclobutanes

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年1月5日

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  • Fuxing Shi,
  • Nils Frank,
  • Markus Leutzsch,
  • Chendan Zhu,
  • Nobuya Tsuji,
  • Benjamin List

摘要

The precise manipulation of unfunctionalized hydrocarbons remains a fundamental challenge for chemical synthesis and catalysis. Stereodifferentiation in strained alkanes is particularly difficult to accomplish because a catalyst has to distinguish various highly exergonic chemo- and stereoselective strain-release channels. Here we disclose an organocatalytic asymmetric hydroalkoxylation of bicyclobutanes with alcohols to efficiently access tertiary cyclopropylcarbinyl ethers with high enantioselectivity (e.r. up to 98:2). Enantiocontrol is accomplished through chiral recognition between the confined iminoimidodiphosphoric acid catalyst and the substrate, mediated by non-covalent interactions between a Lewis basic binding site of the confined anion and the polarized C–H bond of the cyclopropylcarbinyl ion intermediate. Our work establishes bicyclobutane activation by harnessing strain-release energetics while maintaining precise stereo- and regiocontrol through structural confinement.