1. Fe-Catalyzed C–C Bond Construction from Olefins via Radicals
- Author
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Jacob T. Edwards, Chung-Mao Pan, Tian Qin, Yuki Yabe, Patrick L. Holland, Phil S. Baran, Myles W. Smith, Dongyoung Kim, Julian C. Lo, Jinghan Gui, Jessica Giacoboni, and Sara Gutiérrez
- Subjects
Diene ,Free Radicals ,Heteroatom ,Alkenes ,010402 general chemistry ,01 natural sciences ,Biochemistry ,Article ,Catalysis ,Sulfone ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,Organic chemistry ,Sulfones ,Alkyl ,chemistry.chemical_classification ,Olefin fiber ,Molecular Structure ,010405 organic chemistry ,Aryl ,General Chemistry ,Acceptor ,Combinatorial chemistry ,0104 chemical sciences ,chemistry ,Iron Compounds ,Minisci reaction - Abstract
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.
- Published
- 2017