Carbon Dioxide Activation Center (CADIAC), The Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University , Gustav Wieds Vej 14, 8000 Aarhus, Denmark.
Department of Chemistry, Graduate School of Science, Osaka Prefecture University , Sakai, Osaka 599-8531, Japan.
J Am Chem Soc. 2015 Nov 11;137(44):14043-6. doi: 10.1021/jacs.5b09342. Epub 2015 Oct 28.
The first Pd-catalyzed carbonylative couplings of aryl and vinyl halides with vinylogous enolates are reported generating products derived from C-C bond formation exclusively at the γ-position. Good results were obtained with a dienolate derivative of acetoacetate (1,3-dioxin-4-one). These transformations occurred at room temperature and importantly with only stoichiometric carbon monoxide in a two-chamber reactor. The methodology was applied to the synthesis of two members of the statin family generating the cis-3,5-diol acid motif by a γ-selective carbonylation followed by a cis-stereoselective reduction of the 3,5-dicarbonyl acid intermediates.
首次报道了芳基和乙烯基卤化物与乙烯基烯醇盐的 Pd 催化羰基偶联反应，仅在 γ-位生成了 C-C 键形成的产物。乙酸盐（1,3-二氧戊环-4-酮）的二烯醇盐衍生物获得了很好的结果。这些转化在室温下进行，重要的是在两室反应器中仅使用化学计量的一氧化碳即可进行。该方法应用于他汀类药物家族的两个成员的合成，通过γ-选择性羰基化生成顺式-3,5-二醇酸基序，然后对 3,5-二羰基酸中间体进行顺式立体选择性还原。
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