Scholarlink

<p>Although ring-opening reactions of bicyclo[1.1.0]butanes (BCBs) provide a reliable platform for synthesizing functionalized cyclobutanes, current methods frequently encounter challenges such as poor diastereoselectivity, regioselectivity issues, and a lack of α- and β‘-selective transformations. Herein, we report a catalyst-controlled, regiodivergent α- and β‘-selective hydrophosphination of acyl BCBs, which expands the chemical space of tertiary phosphines with multi-substituted cyclobutane backbones derived from identical starting materials. Utilizing a Cu(I) catalytic system, we achieve an α-selective nucleophilic addition to 1,3-disubstituted BCBs. This reaction exhibits a broad substrate scope under mild conditions, yielding valuable 1,1,3-functionalized cyclobutanes predominantly as single diastereoisomers. In contrast, the unusual β‘-selective pathway facilitated by a Cu(II) catalytic system produces 1,2,3-trisubstituted variants with up to &gt;20:1 <i>d.r</i>. The developed method holds promise for accessing structurally diverse cyclobutanes with potential applications in medicinal chemistry and the design of organophosphorus catalysts.</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

Diastereoselective synthesis of multi-substituted cyclobutanes via catalyst-controlled regiodivergent hydrophosphination of acyl bicyclobutanes

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年7月18日

查看全文
  • Heng-Xian He,
  • Feng Wu,
  • Kun-Ju Wang,
  • Lei Wang,
  • Jian-Jun Feng

摘要

Although ring-opening reactions of bicyclo[1.1.0]butanes (BCBs) provide a reliable platform for synthesizing functionalized cyclobutanes, current methods frequently encounter challenges such as poor diastereoselectivity, regioselectivity issues, and a lack of α- and β‘-selective transformations. Herein, we report a catalyst-controlled, regiodivergent α- and β‘-selective hydrophosphination of acyl BCBs, which expands the chemical space of tertiary phosphines with multi-substituted cyclobutane backbones derived from identical starting materials. Utilizing a Cu(I) catalytic system, we achieve an α-selective nucleophilic addition to 1,3-disubstituted BCBs. This reaction exhibits a broad substrate scope under mild conditions, yielding valuable 1,1,3-functionalized cyclobutanes predominantly as single diastereoisomers. In contrast, the unusual β‘-selective pathway facilitated by a Cu(II) catalytic system produces 1,2,3-trisubstituted variants with up to >20:1 d.r. The developed method holds promise for accessing structurally diverse cyclobutanes with potential applications in medicinal chemistry and the design of organophosphorus catalysts.