Department of Chemistry, The Scripps Research Institute , 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Department of Chemistry, Yale University , 225 Prospect Street, New Haven, Connecticut 06520, United States.
J Am Chem Soc. 2017 Feb 15;139(6):2484-2503. doi: 10.1021/jacs.6b13155. Epub 2017 Feb 2.
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.
本文详细介绍了铁催化烯烃向自由基的转化及其在 C-C 键构建中的后续应用。对还原二烯环化的优化导致电子区分的供体和受体烯烃的分子间交叉偶联的发展。尽管供体烯烃上的取代最初仅限于烷基和芳基，但进一步的努力最终使取代范围扩展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，允许高效合成砜加合物，可作为进一步多样化的分支点。此外，这种反应性扩展到基于烯烃的 Minisci 反应中，以官能化杂环支架。最后，通过对反应的深入研究，得到了一个更彻底的反应机制，并由此产生了更高效的第二代烯烃交叉偶联条件。
