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The Development of Novel Electron Transfer Initiated Cyclization (ETIC) Reactions: Discovery of the Diastereoselective ETIC Reaction and Its Application toward the Total Synthesis of Leucascandrolide A

机译:新型电子转移引发环化(ETIC)反应的发展:非对映选择性ETIC反应的发现及其在白藜芦醇A的全合成中的应用

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摘要

The electron transfer initiated cyclization (ETIC) reaction has been shown to provide the efficient formation of cyclic acetals through the selective activation of carbon-carbon [sigma]-bonds. A simple arithmetical equation has been used to design new substrates with enhanced chemoselectivity and reactivity. The ability to design new cyclization substrates has expanded the scope of the ETIC reaction by providing access to more diverse products. Lowering the oxidation potential of the ETIC substrates led to the development of a ground state chemical-mediated protocol. This also allowed for the incorportation of electron rich olefins as carbon-centered nucleophiles. Substrates which undergo endo-cyclizations have shown excellent levels of stereocontrol in the synthesis of syn-2,6-dialkyl tetrahydropyranones, which are useful building blocks in natural product synthesis.A highly stereoselective sequence has been developed for the synthesis of leucascandrolide A with the key transformation utilizing the diastereoselective endo-ETIC reaction. The homopropargylic ether required for installation of the enol acetate was obtained through the stereoselective opening of a cyclic acetal with allenyltributyltin in the presence of a Lewis acid. A metal mediated addition of acetic acid to the alkyne provided the homobenzylic ether with a suitably tethered enol acetate. The enol acetate was then subjected to the chemical mediated ETIC conditions to afford the desired syn-2,6-tetrahydropyranone as a single diastereomer.
机译:已经表明,电子转移引发的环化(ETIC)反应通过碳-碳σ键的选择性活化而提供了环状缩醛的有效形成。一个简单的算术方程已用于设计具有增强的化学选择性和反应性的新底物。设计新环化底物的能力通过提供更多种类的产品,扩大了ETIC反应的范围。降低ETIC基板的氧化电位导致了基态化学介导协议的发展。这也允许富电子烯烃作为碳中心亲核试剂的结合。经过内环化的底物在syn-2,6-二烷基四氢吡喃酮的合成中显示出极好的立体控制水平,这是天然产物合成的有用组成部分。已开发出高度立体选择性的序列,用于合成具有利用非对映选择性内ETIC反应进行关键转化。通过在路易斯酸存在下用烯丙基三丁基锡将环状缩醛立体选择性地打开,获得了安装烯醇乙酸酯所需的均丙炔醚。金属介导的乙酸向炔烃的加成为高苄基醚提供了合适的系链烯醇乙酸酯。然后使烯醇乙酸酯经受化学介导的ETIC条件,以提供所需的作为单一非对映异构体的syn-2,6-四氢吡喃酮。

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    Seiders II John Robert;

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  • 年度 2005
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  • 原文格式 PDF
  • 正文语种 en
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