Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as the Perfluoroalkyl Source

Abstract

An efficient perfluoroalkylation of unactivated alkenes with perfluoro acid anhydrides was developed. Copper salts play a crucial role as a catalyst to achieve allylic perfluoroalkylation with the in situ generated bis(perfluoroacyl) peroxides. Furthermore, carboperfluoroalkylation of alkene bearing an aromatic ring at an appropriate position on the carbon side chain was found to proceed under metal-free conditions to afford carbocycles or heterocycles bearing a perfluoroalkyl group. This method, which makes use of readily available perfluoroalkyl sources, offers a convenient and powerful tool for introducing a perfluoroalkyl group onto an sp(3) carbon to construct synthetically useful skeletons.

Recent Developments in Heck-Type Reaction of Unactivated Alkenes and Alkyl Electrophiles

“…In 2016, the same group realized the trifluoromethylation and perfluoroalkylation of unactivated alkenes (Scheme 22). 40 Different from previous work, they utilized inexpensive trifluoroacetic anhydride (TFAA) as trifluoromethyl source and perfluoroalkyl acid anhydrides possessing a long perfluoroalkyl chain as perfluoroalkyl source. 41 All of internal (e.g., 39a), cyclic (e.g., 39b), and terminal alkenes (e.g., 39c-e) could give the desired products in modest to good yields.…”

Arthur C. Cope Scholar Awards

“…Sie befasst sich mit der Entwicklung von Reaktionen, die auf der Übergangsmetallenolat‐Chemie und der Fluorchemie beruhen, dem Design und der Synthese von Sondenmolekülen auf der Basis von Naturstoffen sowie der Entwicklung neuer Methoden für die Forschung im Bereich der chemischen Biologie. In der Angewandten Chemie beschrieb sie die Perfluoralkylierung nichtaktivierter Alkene . Sodeoka ist Mitglied in den Advisory Boards des Asian Journal of Organic Chemistry , von ChemBioChem und von Chemistry—An Asian Journal .…”

Arthur C. Cope Scholar Awards

“…Sodeoka's research program involves the development of reactions based on transition‐metal enolate chemistry and fluorine chemistry, design and synthesis of probe molecules based on natural products, and the development of new methods for chemical biology research. She has reported in Angewandte Chemie on the perfluoroalkyation of unactivated alkenes . Sodeoka is on the advisory boards of the Asian Journal of Organic Chemistry , ChemBioChem , and Chemistry—An Asian Journal .…”