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<p>In contrast to ynamides, whose chemistry has been extensively explored, ynimines remain underutilized in organic synthesis despite their rich functionalities. Here we report a general strategy to access 2-imido-1,3-dienes, synthetically challenging building blocks, through the reaction of ynimines with carboxylic acids. Leveraging this transformation, we develop a three-component reaction of ynimines, carboxylic acids and electron-deficient alkenes that enables the efficient synthesis of 1-imido-3,4-<i>trans</i>-disubstituted cyclohex-1-enes. The sequence proceeds via regioselective hydroacyloxylation and Mumm rearrangement to generate 2-imido-1,3-dienes, which undergo Diels–Alder cycloadditions. An intramolecular variant furnishes <i>trans</i>-fused tricyclic architectures reminiscent of <i>trans</i>-Δ⁹-tetrahydrocannabinol. Chemoselective hydrolysis further converts 2-imido-1,3-dienes into 2-amido-1,3-dienes, enabling chiral squaramide-catalysed enantioselective Diels–Alder reactions to afford 1-amido-3,4-<i>cis</i>-disubstituted cyclohex-1-enes with high stereocontrol. Distinct concerted and stepwise cycloaddition pathways rationalize the observed stereodivergence.</p>

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Ynimines as versatile precursors to 2-imido- and 2-amido-1,3-dienes for stereodivergent diels–alder reactions

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年3月16日

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  • Ruijia Wang,
  • Xin-Qi Zhu,
  • Maël Djaïd,
  • Rémi Lavernhe,
  • Qian Wang,
  • Jieping Zhu

摘要

In contrast to ynamides, whose chemistry has been extensively explored, ynimines remain underutilized in organic synthesis despite their rich functionalities. Here we report a general strategy to access 2-imido-1,3-dienes, synthetically challenging building blocks, through the reaction of ynimines with carboxylic acids. Leveraging this transformation, we develop a three-component reaction of ynimines, carboxylic acids and electron-deficient alkenes that enables the efficient synthesis of 1-imido-3,4-trans-disubstituted cyclohex-1-enes. The sequence proceeds via regioselective hydroacyloxylation and Mumm rearrangement to generate 2-imido-1,3-dienes, which undergo Diels–Alder cycloadditions. An intramolecular variant furnishes trans-fused tricyclic architectures reminiscent of trans-Δ⁹-tetrahydrocannabinol. Chemoselective hydrolysis further converts 2-imido-1,3-dienes into 2-amido-1,3-dienes, enabling chiral squaramide-catalysed enantioselective Diels–Alder reactions to afford 1-amido-3,4-cis-disubstituted cyclohex-1-enes with high stereocontrol. Distinct concerted and stepwise cycloaddition pathways rationalize the observed stereodivergence.