Feng Wei, Xu Li, Li Deng-Yuan, Liu Pei-Nian
Shanghai Key Laboratory of Functional Materials Chemistry, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Key Laboratory for Advanced Materials and School of Chemistry and Molecular Engineering, East China University of Science and Technology, Meilong Road 130, Shanghai 200237, China.
Org Lett. 2020 Jul 2;22(13):5094-5098. doi: 10.1021/acs.orglett.0c01690. Epub 2020 Jun 17.
Vinylethylene carbonates have been extensively used to trigger [3 + ] or [5 + ] cycloaddition via the formation of η-allylic intermediates, while the important [4 + ] cycloaddition has not been explored yet. Here, we report a new strategy to convert vinylethylene carbonates into 4-(trimethylsilyl)but-2-en-1-ols, which can readily undergo [4 + 2] cycloaddition by in situ formation of 1,3-dienes. This novel reaction involves [Pd]-catalyzed decarboxylative silylation, [Fe]-catalyzed vinylogous Peterson elimination, and subsequent [4 + 2] cycloaddition to afford a multisubstituted cyclohexa-1,4-diene skeleton.
碳酸乙烯基亚乙酯已被广泛用于通过形成η-烯丙基中间体引发[3 + ]或[5 + ]环加成反应，而重要的[4 + ]环加成反应尚未得到探索。在此，我们报道了一种将碳酸乙烯基亚乙酯转化为4-(三甲基甲硅烷基)丁-2-烯-1-醇的新策略，该醇可通过原位形成1,3-二烯轻松进行[4 + 2]环加成反应。这种新颖的反应涉及[Pd]催化的脱羧硅烷化反应、[Fe]催化的插烯式彼得森消除反应，以及随后的[4 + 2]环加成反应，以提供多取代的环己-1,4-二烯骨架。
