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<p>The substitution of classical dienes with C–C bonds in Diels–Alder-type reactions is a compelling paradigm in modern syntheses. Although activation of C–C bonds α to a single heteroatom has been well established, extending this strategy to synthetically valuable C–C moieties α to two heteroatoms remains challenging because of the competing activation of adjacent C–heteroatom bonds. Here we overcome this limitation through the development of a selective C2–C3 bond activation protocol in β-lactams, which operates with remarkable fidelity despite the presence of the intrinsically more reactive N1–C2 bond. Key to this work is the phosphine oxide-ligating Ni–Al bimetallic catalyst system, which positions nickel at C2–C3, suppresses C–N activation and facilitates annulation with diverse <i>π</i>-systems (alkynes/alkenes). This mechanistically guided strategy affords δ-lactam homologues in up to 99% yield, representing a marked departure from conventional cycloaddition approaches constrained by inherent bond reactivity hierarchies.</p><p></p>

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Selective C–C bond cleavage-enabled annulation between β-lactams and π-systems via Ni–Al bimetallic catalysis

  • 期刊论文

  • 发表日期：

    2026年6月3日

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  • Rong-Hua Wang,
  • Wei-Wei Xu,
  • Deng Pan,
  • Yinpeng Wang,
  • Yuzhen Zheng,
  • Cui Yu,
  • Jiang-Fei Li,
  • Tao Zhang,
  • Yi Li,
  • Xiao-Song Xue,
  • Qi-Lin Zhou,
  • Mengchun Ye

摘要

The substitution of classical dienes with C–C bonds in Diels–Alder-type reactions is a compelling paradigm in modern syntheses. Although activation of C–C bonds α to a single heteroatom has been well established, extending this strategy to synthetically valuable C–C moieties α to two heteroatoms remains challenging because of the competing activation of adjacent C–heteroatom bonds. Here we overcome this limitation through the development of a selective C2–C3 bond activation protocol in β-lactams, which operates with remarkable fidelity despite the presence of the intrinsically more reactive N1–C2 bond. Key to this work is the phosphine oxide-ligating Ni–Al bimetallic catalyst system, which positions nickel at C2–C3, suppresses C–N activation and facilitates annulation with diverse π-systems (alkynes/alkenes). This mechanistically guided strategy affords δ-lactam homologues in up to 99% yield, representing a marked departure from conventional cycloaddition approaches constrained by inherent bond reactivity hierarchies.