Cooperative Fe/Co Catalyzed Remote Desaturation for the Synthesis of Unsaturated Amide Derivatives
Year: 2023
Type: preprint
Abstract: Unsaturated amides represent common functional groups found in natural products and bioactive molecules, serving as versatile synthetic building blocks. Here, we report an iron(II)/cobalt(II) dual catalytic system for the syntheses of distally unsaturated amide derivatives. The transformation proceeds through an iron nitrenoid-mediated 1,5-hydrogen atom transfer (1,5-HAT) mechanism. Subsequently, the radical intermediate undergoes hydrogen atom abstraction from the vicinal methylene by a cobaloxime catalyst, efficiently yielding β,γ- or γ,δ-unsaturated amide derivatives under mild conditions. The efficiency of Co-mediated HAT is tunable by varying different auxiliaries, highlighting the generality of this protocol. Remarkably, this desaturation protocol is also amenable to practical scalability, enabling the synthesis of unsaturated carbamates and ureas which can be readily converted into various valuable molecules.
Source: ChemRxiv
Institutions: Utah State University, Columbia University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W4390038473