Synthesis of complex aryl MIDA boronates by Rh-catalyzed [2+2+2] cycloaddition

A Rh-catalyzed [2+2+2] cycloaddition approach for the synthesis of BMIDA-functionalized arenes is reported. The developed method overcomes the long-standing reactivity problems associated with internal alkynes and allows access to highly functionalized borylated benzene scaffolds. The method is broadly functional group tolerant and generally high yielding. The utility of the products is demonstrated through elaboration of the BMIDA motif, and in the synthesis of fused heterocycles via intramolecular Chan-Lam etherification and amination. The dominance of sterically controlled reactivity is described.

Automated summary

A Rh-catalyzed [2+2+2] cycloaddition approach for the synthesis of BMIDA-functionalized arenes is developed to address the reactivity issues associated with internal alkynes. The method enables the access to highly functionalized borylated benzene scaffolds, and exhibits broad functional group compatibility and high yields. The utility of the products is demonstrated through their elaboration and synthesis of fused heterocycles via intramolecular Chan-Lam etherification and amination. The dominance of sterically controlled reactivity is described.