Fe-Catalyzed C–C Bond Construction from Olefins via Radicals

• Published in: Journal of the American Chemical Society 2017-02, Vol.139 (6), p.2484-2503
• Main Authors: Lo, Julian C, Kim, Dongyoung, Pan, Chung-Mao, Edwards, Jacob T, Yabe, Yuki, Gui, Jinghan, Qin, Tian, Gutiérrez, Sara, Giacoboni, Jessica, Smith, Myles W, Holland, Patrick L, Baran, Phil S
• Format: Article
• Language: English
• Subjects: Alkenes - chemistry; Catalysis; Free Radicals - chemistry; Iron Compounds - chemistry; Molecular Structure; Sulfones - chemical synthesis; Sulfones - chemistry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.6b13155

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.