Fe-Catalyzed C-C Bond Construction from Olefins via Radicals.
Fe-Catalyzed C-C Bond Construction from Olefins via Radicals.
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DOI：
10.1021/jacs.6b13155
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发表时间：
2017-02-15
影响因子：
15
通讯作者：
Baran PS
中科院分区：
文献类型：
--
作者：
Lo JC;Kim D;Pan CM;Edwards JT;Yabe Y;Gui J;Qin T;Gutiérrez S;Giacoboni J;Smith MW;Holland PL;Baran PS
这篇文章详细介绍了铁催化的烯烃转化为自由基的发展及其随后在构建C-C键中的应用。对还原二烯环化反应的优化导致了电子分化的给体和受体烯烃分子间交叉偶联的发展。虽然给体烯烃的取代最初仅限于烷基和芳基，但更多的努力最终将取代的范围扩大到各种基于杂原子的官能团，提供了统一的烯烃反应性。开发了一种乙烯基砜受体烯烃，它允许有效地合成可用作进一步多样化的分支点的砜加合物。此外，这种反应性被扩展到基于烯烃的微型反应，以官能化杂环支架。最后，机理研究导致了对反应的更透彻的了解，导致了更有效的第二代烯烃交叉偶联条件的发展。
This Article details the development of the iron-catalyzed conversion of olefins to radicals and their subsequent use in the construction of C–C bonds. Optimization of a reductive diene cyclization led to the development of an intermolecular cross-coupling of electronically-differentiated donor and acceptor olefins. Although the substitution on the donor olefins was initially limited to alkyl and aryl groups, additional efforts culminated in the expansion of the scope of the substitution to various heteroatom-based functionalities, providing a unified olefin reactivity. A vinyl sulfone acceptor olefin was developed, which allowed for the efficient synthesis of sulfone adducts that could be used as branch points for further diversification. Moreover, this reactivity was extended into an olefin-based Minisci reaction to functionalize heterocyclic scaffolds. Finally, mechanistic studies resulted in a more thorough understanding of the reaction, giving rise to the development of a more efficient second-generation set of olefin cross-coupling conditions.