RESUMO
Polyhalogenated biaryls are unique motifs offering untapped potential as versatile building blocks for the expedient synthesis of complex biaryl compounds. Overcoming the limitations of conventional syntheses, we introduce a novel, metal-free, operationally simple and one-pot approach to regioselectively (di)halogenate biaryl compounds under mild conditions using cyclic biaryl hypervalent bromine and chlorine substrates as masked arynes. Through chemoselective post-functionalizations, these valuable products can expand the toolbox for synthesizing biaryl-containing scaffolds, addressing a critical gap in the field.
RESUMO
Enones are widely utilized linchpin functional groups in chemical synthesis and molecular biology. We herein report the direct conversion of boronic esters into enones using commercially available methoxyallene as a three-carbon building block. Following boronate complex formation by reaction of the boronic ester with lithiated-methoxyallene, protonation triggers a stereospecific 1,2-migration before oxidation generates the enone. The protocol shows broad substrate scope and complete enantiospecificity is observed with chiral migrating groups. In addition, various electrophiles could be used to induce 1,2-migration and give a much broader range of α-functionalized enones. Finally, the methodology was applied to a 14-step synthesis of the enone-containing polyketide 10-deoxymethynolide.
