Scholarlink

<p>Developing methods that enable single-atom exchange within an aromatic scaffold, while preserving its peripheral substitution, represents an important but highly ambitious goal in synthesis. In principle, such approaches would allow the impact of a single-atom change within a molecular framework to be distinguished from the effects of also altering the peripheral substituents. Yet despite this conceptual power, single-step methodologies for single-atom exchange in aromatic systems remain rare. Herein, we present a boron-to-carbon swapping reaction via a substituent-rebound process, converting 1,2-benzazaborines into the corresponding quinolines. The employment of glyoxylic acid as the carbon-atom source allows the original substituent on the boron atom to be recaptured and incorporated into the quinoline product, representing a rare example of true single-atom skeletal editing. The transformation exhibits high levels of functional group tolerance and is applicable to the late-stage modifications of natural product and pharmaceutical derivatives. Furthermore, comprehensive mechanistic investigations elucidate the intricacies of this process, establishing a foundation for future single-atom editing manifolds that can facilitate the interrogation of structure–function relationships with atom-level precision.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Substituent-rebound skeletal editing for precise boron-to-carbon single-atom swapping

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2026年7月25日

查看全文
  • Yan-Bo Li,
  • Fu-Peng Wu,
  • Jasper L. Tyler,
  • Constantin G. Daniliuc,
  • Frank Glorius

摘要

Developing methods that enable single-atom exchange within an aromatic scaffold, while preserving its peripheral substitution, represents an important but highly ambitious goal in synthesis. In principle, such approaches would allow the impact of a single-atom change within a molecular framework to be distinguished from the effects of also altering the peripheral substituents. Yet despite this conceptual power, single-step methodologies for single-atom exchange in aromatic systems remain rare. Herein, we present a boron-to-carbon swapping reaction via a substituent-rebound process, converting 1,2-benzazaborines into the corresponding quinolines. The employment of glyoxylic acid as the carbon-atom source allows the original substituent on the boron atom to be recaptured and incorporated into the quinoline product, representing a rare example of true single-atom skeletal editing. The transformation exhibits high levels of functional group tolerance and is applicable to the late-stage modifications of natural product and pharmaceutical derivatives. Furthermore, comprehensive mechanistic investigations elucidate the intricacies of this process, establishing a foundation for future single-atom editing manifolds that can facilitate the interrogation of structure–function relationships with atom-level precision.