Tunable Construction of Multisubstituted 1,3-Dienes and Allenes via a 1,4-Palladium Migration/Carbene Insertion Cascade

Efficient palladium-catalyzed vinylic C-H alkenylation and allenylation of gem-disubstituted ethylenes with N-tosylliydrazones of aryl alkyl and diaryl ketones were achieved to access trisubstituted 1,3-dienes and tetrasubstituted allenes, respectively. An aryl to vinyl 1,4-palladium migration/carbene insertion/beta-hydride elimination sequence proceeded to switch the chemo- and regioselectivities to give structurally diverse products. Use of 2-FC6H2OH additive enables enhancement of the reaction efficiency through accelerating the key 1,4-palladium migration process.

Automated summary

Efficient palladium-catalyzed reactions were utilized to synthesize diverse compounds, including trisubstituted 1,3-dienes and tetrasubstituted allenes. The chemo- and regioselectivities were controlled to obtain structurally diverse products.