Catalytic 1,4-Rhodium(III) Migration Enables 1,3-Enynes to Function as One-Carbon Oxidative Annulation Partners in C?H Functionalizations
Catalytic 1,4-Rhodium(III) Migration Enables 1,3-Enynes to Function as One-Carbon Oxidative Annulation Partners in C?H Functionalizations
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催化 1,4-铑 (III) 迁移使 1,3-烯炔能够作为 C?H 官能化中的一碳氧化成环伙伴
DOI：
10.1002/ange.201406072
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发表时间：
2014
影响因子：
--
通讯作者：
Burns D
中科院分区：
文献类型：
--
作者：
Burns D
在各种铑催化的氧化成环反应中，含顺式烯丙基氢的1，3-烯炔被证明是单碳伙伴，而不是双碳伙伴。这些意想不到的转变的机制，提出通过双C H激活发生，涉及到迄今罕见的例子的1，4-迁移的RhIII物种。这种现象在各种底物中是普遍的，并提供了各种各样的杂环产物。
1,3‐Enynes containing allylic hydrogens cis to the alkyne are shown to act as one‐carbon partners, rather than two‐carbon partners, in various rhodium‐catalyzed oxidative annulations. The mechanism of these unexpected transformations is proposed to occur through double CH activation, involving a hitherto rare example of the 1,4‐migration of a RhIIIspecies. This phenomenon is general across a variety of substrates, and provides a diverse range of heterocyclic products.