Palladium-Catalyzed Carbonylative Couplings of Vinylogous Enolates: Application to Statin Structures
Palladium-Catalyzed Carbonylative Couplings of Vinylogous Enolates: Application to Statin Structures
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DOI：
10.1021/jacs.5b09342
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发表时间：
2015-11-11
影响因子：
15
通讯作者：
Skrydstru, Troels
中科院分区：
文献类型：
--
作者：
Makarov, Ilya S.;Kuwahara, Takashi;Skrydstru, Troels
首次报道了钯催化的芳基和乙烯基卤化物与乙烯基烯醇化物的羰基化偶联反应，生成的产物仅在γ-位形成C-C键。用乙酰乙酸酯（1，3-二恶英-4-酮）的二烯醇衍生物获得了良好的结果。这些转变发生在室温下，重要的是，在两室反应器中只有化学计量的一氧化碳。该方法被应用到合成的他汀类药物家族的两个成员产生的顺式-3，5-二醇酸基序的γ-选择性羰基化，然后由顺式立体选择性还原的3，5-二羰基酸中间体。
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 gamma-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 gamma-selective carbonylation followed by a cis-stereoselective reduction of the 3,5-dicarbonyl acid intermediates.