Access to and unexplored reactivity of nickel-bound 5-membered O- and N-heterocyclic arynes via computational insight
Year: 2026
Type: article
Abstract: metal back-donation and thereby enable formation of otherwise inaccessible 5-membered heterocyclic arynes. Interestingly, heterocycles such as 4-azaindole and benzofuran that lacked subtle steric interactions were found to form borate complexes instead of the desired aryne during the key transmetallation step. Herein, we employ a computationally guided ligand approach to overcome this borate complex formation to generate the desired arynes. Using our computational findings, we accessed new previously inaccessible arynes: 4-azaindol-2,3-yne, pyrrolo-2,3-yne pyrazine, and the first ever proposed aryne, benzofuran-2,3-yne, all bound to Ni. Additionally, we report on a novel 5-membered aryne mode of reactivity in the form of a formal inverse-demand Diels-Alder reaction to yield a new class of underexplored heterocycles.
Source: Chemical Science
DOI: 10.1039/d6sc05533h
Institutions: University of Minnesota, Oberlin College
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: diamond
Awards: Track 4: Advanced CI Coordination Ecosystem: Monitoring and Measurement Services, CAREER: Understanding and Directing Selectivity in Functionalizations of Strong Covalent Bonds Utilizing Coordination-Sphere Effects, Track 1: ACCESS Resource Allocations Marketplace and Platform Services (RAMPS), Graduate Research Fellowship Program (GRFP), ACO: An Open CI Ecosystem to Advance Scientific Discovery (OpenCI), Track 3: COre National Ecosystem for CyberinfrasTructure (CONECT), Upgrade of a 500 MHz NMR Spectrometer for Applications in Biomedical Research, G5249530352, Track 2: Customized Multi-tier Assistance, Training, and Computational Help (MATCH) for End User ACCESS to CI, Methods for Selective Functionalization of (Hetero)arene Rings
OpenAlex ID: W7213195730