Xin Tiansi, Cummins Christopher C
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
J Am Chem Soc. 2023 Dec 6;145(48):25989-25994. doi: 10.1021/jacs.3c11263. Epub 2023 Nov 27.
We report the first synthesis and structural characterization of free, uncomplexed phosphet-2-ones. These unsaturated four-membered phosphacycles were prepared by phosphinidene transfer from dibenzo-7-phosphanorbornadiene compounds, RP ( = CH, anthracene), to cyclopropenones in yields of up to 89%. Theoretical studies suggest that the reaction proceeds through ketene-ylide and ketene-phosphaalkene intermediates. Further transformations of the phosphet-2-ones led to the isolation of more phosphet-2-ones and 1,2-dihydrophosphetes, including two furanone derivatives which are postulated to be produced by intramolecular phosphine-catalyzed [3 + 2] annulations.
我们报道了游离、未络合的磷杂环丁-2-酮的首次合成及结构表征。这些不饱和四元磷杂环是通过二苯并-7-磷杂降冰片二烯化合物RP(=CH,蒽)的磷烯转移反应制备得到的，反应生成环丙烯酮，产率高达89%。理论研究表明，该反应通过乙烯酮叶立德和乙烯酮磷杂烯烃中间体进行。磷杂环丁-2-酮的进一步转化导致分离出更多的磷杂环丁-2-酮和1,2-二氢磷杂环丁二烯，其中包括两种呋喃酮衍生物，据推测它们是由分子内膦催化的[3+2]环化反应生成的。
