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<p>The α-C-C cleavage coupling of ketones offers a highly challenging yet promising approach for C–C bond formation, particularly given the ubiquity and ready accessibility of ketones as fundamental synthons in organic synthesis. However, the deacylative cross-coupling between two distinct ketones via a single activation mode remains an unmet challenge, although this coupling paradigm could be leveraged to construct C(sp<sup>3</sup>)–C(sp<sup>3</sup>) linkages with exceptional structural diversity. Herein, we describe a cross-ketone deacylative coupling via nickel-catalyzed bimolecular homolytic substitution (S<sub>H</sub>2), in which the synergistic oxidative photocatalysis is combined to produce simultaneously two distinct open-shell carbons from ketone-derived dihydroquinazolinones. This hetero-selective radical-radical coupling protocol enables the construction of quaternary carbon centers through a critical S<sub>H</sub>2 displacement mechanism, providing an efficient approach to furnish β-quaternary aliphatic amines. Additionally, a wide array of biorelevant small molecules, including β-amino alcohol, β-diamine and β-aminothiol derivatives, can also be obtained via this cross-double deacylative C<sub>1</sub>-alkylation approach between distinct ketones.</p>

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Cross-ketone deacylative coupling via oxidative SH2 homolytic substitution

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年3月19日

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  • Jian-Xiong Yang,
  • Meng-Yao Zhang,
  • Qi Wen,
  • Jia-Run Wang,
  • Yan Zhang,
  • Heng Jiang

摘要

The α-C-C cleavage coupling of ketones offers a highly challenging yet promising approach for C–C bond formation, particularly given the ubiquity and ready accessibility of ketones as fundamental synthons in organic synthesis. However, the deacylative cross-coupling between two distinct ketones via a single activation mode remains an unmet challenge, although this coupling paradigm could be leveraged to construct C(sp3)–C(sp3) linkages with exceptional structural diversity. Herein, we describe a cross-ketone deacylative coupling via nickel-catalyzed bimolecular homolytic substitution (SH2), in which the synergistic oxidative photocatalysis is combined to produce simultaneously two distinct open-shell carbons from ketone-derived dihydroquinazolinones. This hetero-selective radical-radical coupling protocol enables the construction of quaternary carbon centers through a critical SH2 displacement mechanism, providing an efficient approach to furnish β-quaternary aliphatic amines. Additionally, a wide array of biorelevant small molecules, including β-amino alcohol, β-diamine and β-aminothiol derivatives, can also be obtained via this cross-double deacylative C1-alkylation approach between distinct ketones.