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Pd0-Catalyzed Formal 1,3-Diaza-Claisen Rearrangement. Design And Development Of Cationic 1,3-Diaza-Claisen Rearrangement., Yanbo Yang

Graduate College Dissertations and Theses

The dissertation describes Pd⁰-catalyzed formal 1,3-diaza-Claisen rearrangement and the design and development of cationic 1,3-diaza-Claisen rearrangement.

Our previous work has shown that isocyanates react with azanorbornenes and azabicyclo[2.2.2]octenes under thermal conditions to afford zwitterionic intermediates that undergo a thermal 1,3-diaza-Claisen rearrangement to give both ureas and isoureas. However, some azanorbornenes and azabicyclooctenes failed to rearrange or proceeded in low yields. To address these challenging substrates for the thermal 1,3-diaza-Claisen rearrangement, we have developed a Pd⁰-catalyzed formal 1,3-diaza-Claisen rearrangement. Interestingly, under Pd⁰-catalyzed condition, both isocyanates with electron-withdrawing groups and isocyanates without electron-withdrawing groups react with …