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<p>The [2π+2σ] cycloaddition reaction between bicyclobutanes (BCBs) and C=X (where X = C or heteroatom) coupling partners is a reliable method to efficiently construct (hetero)bicyclo[2.1.1]hexane (BCH) frameworks. However, similar reactions involving C≡C triple bonds for synthesizing valuable bicyclo[2.1.1]hexenes (BCHes), particularly with arynes, are extremely rare due to the competing favorable Alder-Ene reaction. Here we report a silver-catalyzed dearomative [2π+2σ] cycloaddition/rearomatization strategy for the modular synthesis of functionalized benzobicyclo[2.1.1]hexene derivatives (Benzo-BCHes). Using AgBF as the catalyst and with naphthols serving as surrogates for arynes, the reaction proceeded with high chemoselectivity to generate Benzo-BCHs, achieving up to 83% yield despite competing with at least five side reactions. The protocol exhibits a broad substrate scope, excellent functional group tolerance, versatile functionalization of the products, and scalable synthesis, thereby underscoring its practical utility for the construction of complex Benzo-BCH structures. Density functional theory (DFT) computations offer mechanistic insights into the cycloaddition/rearomatization process, and aromaticity modulation in annelated naphthalenes, and elucidate the origin of observed chemoselectivity.</p>

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Silver-catalyzed formal [2π+2σ] cycloaddition of bicyclobutanes with naphthols as surrogates for arynes

  • 期刊论文

  • 发表日期：

    2025年7月4日

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  • Lei Tang,
  • Kun-Ju Wang,
  • Lei Wang,
  • Fujian Yang,
  • Quanxin Peng,
  • Guoqiang Wang,
  • Jian-Jun Feng

摘要

The [2π+2σ] cycloaddition reaction between bicyclobutanes (BCBs) and C=X (where X = C or heteroatom) coupling partners is a reliable method to efficiently construct (hetero)bicyclo[2.1.1]hexane (BCH) frameworks. However, similar reactions involving C≡C triple bonds for synthesizing valuable bicyclo[2.1.1]hexenes (BCHes), particularly with arynes, are extremely rare due to the competing favorable Alder-Ene reaction. Here we report a silver-catalyzed dearomative [2π+2σ] cycloaddition/rearomatization strategy for the modular synthesis of functionalized benzobicyclo[2.1.1]hexene derivatives (Benzo-BCHes). Using AgBF as the catalyst and with naphthols serving as surrogates for arynes, the reaction proceeded with high chemoselectivity to generate Benzo-BCHs, achieving up to 83% yield despite competing with at least five side reactions. The protocol exhibits a broad substrate scope, excellent functional group tolerance, versatile functionalization of the products, and scalable synthesis, thereby underscoring its practical utility for the construction of complex Benzo-BCH structures. Density functional theory (DFT) computations offer mechanistic insights into the cycloaddition/rearomatization process, and aromaticity modulation in annelated naphthalenes, and elucidate the origin of observed chemoselectivity.