CO2 As A Transient Directing Group for the Oxidative Heck Coupling of Free Allylamines With Aryl Iodides
Year: 2020
Type: preprint
Abstract: Oxidative Heck couplings are a powerful method for elaborating alkene feedstocks. While selective functionalization of terminal olefins has been achieved by catalyst design, selective functionalization of internal olefins has generally required use of directing groups except in the case of Michael acceptors. Allylamine substrates have typically required protection to be suitable for these reactions, decreasing the step and atom economy of these procedures. Herein we demonstrate that the addition of CO 2 (dry ice) as a transient directing group allows for the stereospecific arylation of both secondary and primary allylamines in the presence of a Pd II catalyst. Notably, the product 3,3’-diarylallylamine motif is prevalent in a variety of biologically-relevant structures, and this method represents the most straightforward synthesis of these targets to date. Key features of the method are the ability to access relatively mild conditions that facilitate a broad substrate scope, as well as direct diarylation of terminal allylamine substrates. In addition, several complex and therapeutically-relevant molecules are included to demonstrate the utility of the transformation.
Source: ChemRxiv
Authors: Vinod Landge, Justin Maxwell, Pratibha Chand-Thakuri, Mohit Kapoor, Evan Diemler, Michael Young
Institution: University of Toledo
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Award: G8021022995
OpenAlex ID: W4241202823