Scholarlink

<p>The most established reactivity of [1.1.1]propellane involves addition reactions at the bridge C-C bond, resulting in the formation of bicyclo[1.1.1]pentane derivatives. Herein, we present a [2,3]-sigmatropic rearrangement that uses [1.1.1]propellane as a carbene precursor to rapidly access allenylated or allylated methylenecyclobutanes. The reaction is highly efficient and scalable, works well under mild conditions, and can tolerate a diverse range of functional groups on propargyl and allyl sulfides/selenides. Another significant achievement of this approach is the utility of the obtained products in synthesizing substituted bicyclo[2.1.1]hexanes, potential bioisosteres of <i>ortho</i> and <i>meta</i>-substituted benzenes, by developing a photocatalyzed radical cascade cyclization. Density functional theory calculations suggest the involvement of a copper-bound five-membered transition state.</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

[2,3]-Sigmatropic rearrangement with [1.1.1]propellane

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2025年7月7日

查看全文
  • Suparnak Midya,
  • Aksar Ali,
  • Durga Prasad Hari

摘要

The most established reactivity of [1.1.1]propellane involves addition reactions at the bridge C-C bond, resulting in the formation of bicyclo[1.1.1]pentane derivatives. Herein, we present a [2,3]-sigmatropic rearrangement that uses [1.1.1]propellane as a carbene precursor to rapidly access allenylated or allylated methylenecyclobutanes. The reaction is highly efficient and scalable, works well under mild conditions, and can tolerate a diverse range of functional groups on propargyl and allyl sulfides/selenides. Another significant achievement of this approach is the utility of the obtained products in synthesizing substituted bicyclo[2.1.1]hexanes, potential bioisosteres of ortho and meta-substituted benzenes, by developing a photocatalyzed radical cascade cyclization. Density functional theory calculations suggest the involvement of a copper-bound five-membered transition state.