Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide N -Aryl ketenimines have been established as highly reactive aza-dienophiles. Intermolecular cycloadditions are achieved upon heating in the presence of 2,5-bis(silyloxy)furans and proceed with high levels of peri-, regio-, chemo- and diastereo-selectivity. Spontaneous C–O cleavage yields oxygenated pyridone derivatives in a highly convergent and redox-neutral manner. Combined experimental and computational studies demonstrate N -aryl ketenimines to be significantly more reactive than imino dienophiles, as a consequence of less distorted transition states. Derivatization studies include the development of isocyanate and cyclic ketenimine equivalents as aza-dienophiles, while extension to a one-pot aza-Diels–Alder/oxa-Diels–Alder sequence provides a three-component approach to complex fused pyridone/pyran systems.
DOI: 10.1021/jacs.4c17174
Institutions: University of Georgia, University of California, Los Angeles
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: CAREER: New Pericyclic Methodologies for the Convergent Synthesis of Complex Ring Systems, 12 T FTICR-MS System for the Analysis of Metabolites, G575095112, Experimental and Theoretical Investigations of Organic Reaction Rates and Mechanisms, G8590606064, Purchase of a Thermo Fisher Scientific LTQ Orbitrap XL Mass Spectrometer
OpenAlex ID: W4407233598