Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide We previously reported the synthesis of an inaccessible 7-aza-2,3-indolyne through the stabilization of interactions with nickel. This was achieved via intramolecular Suzuki coupling (i.e., oxidative addition and transmetalation) with ortho -borylaryl bromide derivatives of 7-azaindole. Many questions remained about the electronic structure of this complex, which herein we sought to answer through XPS studies. We also sought to expand the strategy to additional inaccessible five-membered heteroarynes and gain insights into factors that lead to successful aryne formation. Several new classes of heteroarynes derived from indole, pyrrolopyrimidine, and the remaining isomers of azaindole were accessed. Transmetalation studies show that aryne formation depends on the identity of the heteroarene. A borate complex of 4-azaindole was isolated and characterized via NMR spectroscopy and crystallographically. This complex could be promoted to undergo transmetalation through the installation of an electron-donating substituent, which was justified computationally. To demonstrate the utility of heteroarynes as a newly accessible functional group, a one-pot difunctionalization was achieved across these classes of heterocycles using newly accessible heteroaryne complexes.
Source: JACS Au
Institutions: University of Minnesota, Oberlin College
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $3,500
Funders: National Science Foundation, Alfred P. Sloan Foundation, Camille and Henry Dreyfus Foundation, Amgen, Bristol-Myers Squibb, McKnight Foundation, University of Minnesota, National Institutes of Health, Materials Research Science and Engineering Center, Harvard University, National Institute of General Medical Sciences, Division of Materials Research, Office of Advanced Cyberinfrastructure, Division of Electrical, Communications and Cyber Systems, Division of Chemistry, National Science Foundation Graduate Research Fellowship Program
Awards: MRI: Acquisition of a MALDI-TOF/TOF Mass Spectrometer for Molecular Structure Determination and Imaging, G1405578316, G1453181110, G1555197637, G1633942665, G1787346651, G1801249269, MRI: Acquisition of a high-performance computing cluster to enhance undergraduate research and education across the sciences at Oberlin College, Track 4: Advanced CI Coordination Ecosystem: Monitoring and Measurement Services, G205304414, G259601046, CAREER: Understanding and Directing Selectivity in Functionalizations of Strong Covalent Bonds Utilizing Coordination-Sphere Effects, G310967942, G3270376671, G3309432434, G338811424, G3406661761, G34258105, G3562386289, Track 1: ACCESS Resource Allocations Marketplace and Platform Services (RAMPS), G4010157413, G403942265, Graduate Research Fellowship Program (GRFP), G4275568664, G4456596007, G4470453470, G4489968610, ACO: An Open CI Ecosystem to Advance Scientific Discovery (OpenCI), G4732505172, G5050677891, Track 3: COre National Ecosystem for CyberinfrasTructure (CONECT), Upgrade of a 500 MHz NMR Spectrometer for Applications in Biomedical Research, G5156331529, G5212984984, G5367127336, G5373507601, G5464919783, G6121277264, G6543735977, G6965887028, G6995829561, MRI: Acquisition of a single-crystal diffractometer for the University of Minnesota, G7054150439, G7526614437, G754684247, G7573957695, G7916508619, G8174472116, Track 2: Customized Multi-tier Assistance, Training, and Computational Help (MATCH) for End User ACCESS to CI, G8499740153, University of Minnesota Materials Research Science and Engineering Center, G867948759, NNCI: Midwest Nano Infrastructure Corridor (MINIC), G8928599955, G8994211811, Methods for Selective Functionalization of (Hetero)arene Rings
OpenAlex ID: W4414495871