Reported herein are the bench stable (24)-diazohexa-2,4-dienals (diazodienals) and their unprecedented polycyclization with aldimine and arylamines enabled by Rh(II)/Brønsted acid relay catalysis. This scalable and atom-economical reaction provides direct access to the biologically important azatricyclo[6.2.1.0]undecane fused polycycles having six-contiguous stereocenters. Mechanistic studies revealed that polycyclization proceeds through an unusual triple-nucleophilic cascade initiated by aldimine attack on remote Rh-carbenoid, 6π-electrocyclization of aza-trienyl azomethine ylide, stereoselective aza-Michael addition via iminium activation, and inverse electron-demand intramolecular aza Diels-Alder reaction. The π-π secondary interactions play a crucial role in the preorganization of reactive intermediates for the pericyclic reactions and, hence, the overall efficiency of the polycyclization.
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| http://dx.doi.org/10.1021/jacsau.4c00134 | DOI Listing |
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