Eckart-Frank Isaiah K, Wilkerson-Hill Sidney M
Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States.
J Am Chem Soc. 2023 Aug 23;145(33):18591-18597. doi: 10.1021/jacs.3c05699. Epub 2023 Aug 8.
Herein, we demonstrate the use of / mixtures of α,α-disubstituted crotylhydrazones to obtain spirocyclic vinylcyclobutanes in a diastereoselective fashion. We show 24 examples of a 1,1-insertion/4--trig tandem process to produce these motifs. Additionally, spirocyclic alkylidene cyclobutanes can be obtained by using α,α-disubstituted allylated hydrazones (11 examples). In this study, we show that the aryl migrating group has a dramatic impact on the course of the reaction. Specifically, allylic C-H insertion products can be obtained in good yields using bromoenones as reaction partners. When Pd(0) is used with no aryl or alkenyl bromide, an intramolecular cyclopropanation reaction takes place to afford [2.1.0]-bicycles.
在此，我们展示了使用α,α-二取代巴豆腙/混合物以非对映选择性方式获得螺环乙烯基环丁烷。我们展示了24个通过1,1-插入/4-三取代串联过程生成这些结构单元的例子。此外，使用α,α-二取代烯丙基化腙可得到螺环亚烷基环丁烷（11个例子）。在本研究中，我们表明芳基迁移基团对反应进程有显著影响。具体而言，使用溴代烯酮作为反应伙伴可以高收率获得烯丙基C-H插入产物。当不使用芳基或烯基溴而使用Pd(0)时，会发生分子内环丙烷化反应以得到[2.1.0]双环化合物。
