Tyler Jasper L, Schäfer Felix, Shao Huiling, Stein Colin, Wong Audrey, Daniliuc Constantin G, Houk K N, Glorius Frank
Organisch-Chemisches Institut, Universität Münster, 48149 Münster, Germany.
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, United States.
J Am Chem Soc. 2024 Jun 12;146(23):16237-16247. doi: 10.1021/jacs.4c04403. Epub 2024 May 29.
As the chemistry that surrounds the field of strained hydrocarbons, such as bicyclo[1.1.0]butane, continues to expand, it becomes increasingly advantageous to develop alternative reactivity modes that harness their unique properties to access new regions of chemical space. Herein, we report the use of photoredox catalysis to promote the single-electron oxidation of bicyclo[1.1.0]butanes. The synthetic utility of the resulting radical cations is highlighted by their ability to undergo highly regio- and diastereoselective [2π + 2σ] cycloaddition reactions. The most notable feature of this transformation is the breadth of alkene classes that can be employed, including nonactivated alkenes, which have so far been elusive for previous strategies. A rigorous mechanistic investigation, in conjunction with DFT computation, was undertaken in order to better understand the physical nature of bicyclo[1.1.0]butyl radical cations and thus provides a platform from which further studies into the synthetic applications of these intermediates can be built upon.
随着围绕诸如双环[1.1.0]丁烷等张力烃领域的化学不断拓展，开发利用其独特性质以进入化学空间新区域的替代反应模式变得越来越具有优势。在此，我们报道了使用光氧化还原催化来促进双环[1.1.0]丁烷的单电子氧化。所得自由基阳离子能够进行高度区域和非对映选择性的[2π + 2σ]环加成反应，这突出了其合成效用。这种转化最显著的特点是可使用的烯烃种类广泛，包括非活化烯烃，而这在以前的策略中一直难以实现。为了更好地理解双环[1.1.0]丁基自由基阳离子的物理性质，我们结合密度泛函理论计算进行了严格的机理研究，从而为进一步研究这些中间体的合成应用提供了一个平台。
