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<p>The development of organo-catalyzed C(sp<sup>2</sup>)–O functionalization has gained significant importance in modern synthetic chemistry. However, a practical and general strategy for constructing chiral molecules via this approach remains elusive. Here we report an organo-catalyzed enantioselective formal C(sp<sup>2</sup>)–O/O–H cross metathesis using alcohols as nucleophiles and boron dipyrromethene (BODIPY) dyes as a class of valuable substrates to validate this concept. A series of boron-stereogenic <i>α,α</i>-di-alkyloxyl/aryloxyl BODIPYs have been achieved in up to 97% yields with 99.8% ee. Notably, detailed mechanistic studies reveal the crucial roles of both nucleophile and leaving-group, suggesting that the reaction might proceed via a concerted nucleophilic aromatic substitution pathway. Computational studies further indicate potential interactions among the BODIPY substrate, nucleophile, and chiral catalyst through multiple hydrogen bonds, achieving excellent enantioselectivity via a proton-transfer process. Moreover, these chiral BODIPY derivatives exhibit promising photophysical properties, highlighting their potential as chiral fluorescent probes or optoelectronic materials.</p>

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Construction of boron-stereogenic BODIPYs through organo-catalyzed enantioselective formal C(sp2)–O/O–H metathesis

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月11日

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  • Jia-Le Zhang,
  • Juan Ma,
  • Luying Guo,
  • Yuefei Hu,
  • Shiqing Huang,
  • Erhong Hao,
  • Zhong-Yuan Li

摘要

The development of organo-catalyzed C(sp2)–O functionalization has gained significant importance in modern synthetic chemistry. However, a practical and general strategy for constructing chiral molecules via this approach remains elusive. Here we report an organo-catalyzed enantioselective formal C(sp2)–O/O–H cross metathesis using alcohols as nucleophiles and boron dipyrromethene (BODIPY) dyes as a class of valuable substrates to validate this concept. A series of boron-stereogenic α,α-di-alkyloxyl/aryloxyl BODIPYs have been achieved in up to 97% yields with 99.8% ee. Notably, detailed mechanistic studies reveal the crucial roles of both nucleophile and leaving-group, suggesting that the reaction might proceed via a concerted nucleophilic aromatic substitution pathway. Computational studies further indicate potential interactions among the BODIPY substrate, nucleophile, and chiral catalyst through multiple hydrogen bonds, achieving excellent enantioselectivity via a proton-transfer process. Moreover, these chiral BODIPY derivatives exhibit promising photophysical properties, highlighting their potential as chiral fluorescent probes or optoelectronic materials.