Modular synthesis of stereodefined benzocyclobutene derivatives via sequential Cu- and Pd-catalysis

Benzocyclobutenes (BCBs) are of growing interest in materials and medicinal chemistry, although general routes for their provision remain underexplored. A modular, divergent and stereoselective Cu- and Pd-catalyzed assembly/cyclization sequence allows the synthesis of densely functionalized BCBs, from readily accessible imine, allene and diboron precursors. Preliminary results have identified enantioselective conditions for our protocol, and highlighted, for example, its applicability to the synthesis of BCBcontaining peptides. By simple variation of experimental conditions or substrate modification, our strategy was expanded to deliver indoline and quinoline derivatives, suitable for further manipulations.