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<p>In sharp contrast to 1,2-rearrangement, a concerted 1,3-alkyl shift is generally not feasible due to the antiaromatic 4<i>π</i> Hückel transition state and geometric strain. Existing stepwise approaches, which involve radical and organometallic intermediates, often lead to racemization of the migrating atom’s stereocentre and suffer from the highly competitive β-hydride elimination reaction. Theoretically, two consecutive 1,2-shifts could produce the same product as a direct 1,3-migration. Specifically, two scenarios are possible: two successive migrations of the same atom or sequential migrations of two different bonding atoms. Here we report the realization of this strategy by integrating a palladium-catalysed semi-pinacol rearrangement with a 1,2-C/Pd(IV) dyotropic rearrangement. We demonstrate that two distinct 1,3-shift products can be selectively obtained by controlling the conformation of the Pd(II) intermediate, which can in turn be modulated by the metal’s supporting ligand. A key feature of this methodology is that the absolute configuration of the migrating group is retained, an outcome unachievable with existing strategies.</p><p></p>

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Concerted 1,3-migration through regiodivergent consecutive 1,2-rearrangements using palladium catalysis

  • 期刊论文

  • 发表日期：

    2026年1月30日

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  • Jing Gong,
  • Qian Wang,
  • Jieping Zhu

摘要

In sharp contrast to 1,2-rearrangement, a concerted 1,3-alkyl shift is generally not feasible due to the antiaromatic 4π Hückel transition state and geometric strain. Existing stepwise approaches, which involve radical and organometallic intermediates, often lead to racemization of the migrating atom’s stereocentre and suffer from the highly competitive β-hydride elimination reaction. Theoretically, two consecutive 1,2-shifts could produce the same product as a direct 1,3-migration. Specifically, two scenarios are possible: two successive migrations of the same atom or sequential migrations of two different bonding atoms. Here we report the realization of this strategy by integrating a palladium-catalysed semi-pinacol rearrangement with a 1,2-C/Pd(IV) dyotropic rearrangement. We demonstrate that two distinct 1,3-shift products can be selectively obtained by controlling the conformation of the Pd(II) intermediate, which can in turn be modulated by the metal’s supporting ligand. A key feature of this methodology is that the absolute configuration of the migrating group is retained, an outcome unachievable with existing strategies.