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<p>Alkynylallylic substitution has emerged as a new and reliable model for the construction of 1,4-enyne skeletons. However, this method is limited to regiospecific S<sub><i>N</i></sub>2′ coupling due to favorable stereocontrol in a small reaction pocket. Here, we demonstrate that the regioselectivity for the transformation can be dictated to occur at the <i>in situ</i> position, and thus achieve the unprecedented remote alkynylallylic substitution. BOX ligands instead of commonly used PyBOX are adopted for Cu metal to guarantee the high remote regioselectivity, and the protocol is suitable for diverse <i>N</i>-, <i>O</i>-, and <i>C</i>-based nucleophiles. More challenging, the asymmetric protocol for <i>in situ</i> remote substitution is established through precise regio- and enantiocontrol via Cu/FOXAP catalysis. Mechanistic studies suggest that a monocopper ligated with multiple ligands might be involved in the enantio-determining step and the cleavage of the remote leaving group works as the rate-determining step.</p>

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Asymmetric remote alkynylallylic substitution via copper catalysis

  • 期刊论文

  • 发表日期：

    2026年2月6日

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  • Zi-Han Li,
  • Hong-Die Zeng,
  • Han-Yu Lu,
  • Guo-Qiang Lin,
  • Zhi-Tao He

摘要

Alkynylallylic substitution has emerged as a new and reliable model for the construction of 1,4-enyne skeletons. However, this method is limited to regiospecific SN2′ coupling due to favorable stereocontrol in a small reaction pocket. Here, we demonstrate that the regioselectivity for the transformation can be dictated to occur at the in situ position, and thus achieve the unprecedented remote alkynylallylic substitution. BOX ligands instead of commonly used PyBOX are adopted for Cu metal to guarantee the high remote regioselectivity, and the protocol is suitable for diverse N-, O-, and C-based nucleophiles. More challenging, the asymmetric protocol for in situ remote substitution is established through precise regio- and enantiocontrol via Cu/FOXAP catalysis. Mechanistic studies suggest that a monocopper ligated with multiple ligands might be involved in the enantio-determining step and the cleavage of the remote leaving group works as the rate-determining step.