Catalytic generation of ortho-quinone dimethides via donor/donor rhodium carbenes† † Electronic supplementary information (ESI) available. CCDC 2087127–2087130, 2087132–2087135, 2087415, 2145030, 2240749. For ESI and crystallographic data in CIF or other electronic format see DOI: https://doi.org/10.1039/d3sc00734k

ABSTRACT: Substrates engineered to undergo a 1,4-C–H insertion to yield benzocyclobutenes resulted in a novel elimination reaction to yield ortho-quinone dimethide (o-QDM) intermediates that undergo Diels–Alder or hetero-Diels–Alder cycloadditions. The analogous benzylic acetals or ethers avoid the C–H insertion pathway completely and, after hydride transfer, undergo a de-aromatizing elimination reaction to o-QDM at ambient temperature. The resulting dienes undergo a variety of cycloaddition reactions with high diastereo- and regio-selectivity. This is one of the few examples of catalytic generation of o-QDM without the intermediacy of a benzocyclobutene and represents one of the mildest, ambient temperature processes to access these useful intermediates. This proposed mechanism is supported by DFT

SUBMITTER: Gao M 

PROVIDER: S-EPMC10266466 | biostudies-literature | 2023 May

REPOSITORIES: biostudies-literature