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<p>Allylic ethers and alcohols are essential structural motifs commonly present in natural products and pharmaceuticals. Direct allylic C–H oxygenation of internal alkenes is one of the most direct methods, bypassing the necessity for an allylic leaving group that is needed in the traditional Tsuji–Trost reaction. Herein, we develop an efficient and practical method for synthesizing (<i>E</i>)-allyl ethers from readily available internal alkenes and alcohols or phenols via selective allylic C–H oxidation. Key advances include the use of a Cu/Azodiformate catalyst system to facilitate remote allylic C–H activation and the achievement of excellent chemoselectivity through a dynamic ligand exchange strategy using a bis(sulfonamide) ligand. This method features a broad substrate scope and functional group tolerance, successfully applied to the synthesis of various challenging medium-sized cyclic ethers (7-10 members) and large-ring lactones (14-20 members), with high regioselectivity and stereoselectivity.</p>

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Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年1月20日

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  • Le Wang,
  • Yuan She,
  • Jie Xiao,
  • Zi-Hao Li,
  • Shen-Yuan Zhang,
  • Peng-Fei Lian,
  • Tong-Mei Ding,
  • Shu-Yu Zhang

摘要

Allylic ethers and alcohols are essential structural motifs commonly present in natural products and pharmaceuticals. Direct allylic C–H oxygenation of internal alkenes is one of the most direct methods, bypassing the necessity for an allylic leaving group that is needed in the traditional Tsuji–Trost reaction. Herein, we develop an efficient and practical method for synthesizing (E)-allyl ethers from readily available internal alkenes and alcohols or phenols via selective allylic C–H oxidation. Key advances include the use of a Cu/Azodiformate catalyst system to facilitate remote allylic C–H activation and the achievement of excellent chemoselectivity through a dynamic ligand exchange strategy using a bis(sulfonamide) ligand. This method features a broad substrate scope and functional group tolerance, successfully applied to the synthesis of various challenging medium-sized cyclic ethers (7-10 members) and large-ring lactones (14-20 members), with high regioselectivity and stereoselectivity.