Palladium-catalysed asymmetric annulations of Morita-Baylis-Hillman carbonates with allenes or alkenes <i>via</i> migratory insertion.

ABSTRACT: As one of the most versatile intermediates in organic synthesis, π-allylpalladium complexes have been extensively exploited in allylic alkylation reactions with a wide range of nucleophiles. In contrast, their engagement in the migratory insertion process remains significantly underdeveloped. Here we demonstrate that the π-allylpalladium intermediates derived from Pd⁰ and Morita-Baylis-Hillman (MBH) carbonates of activated ketones can isomerize to the corresponding η¹-form when stabilised by a pendent carbonyl group, and undertake migratory insertion into various allenes and even styrene-type alkenes efficiently. Subsequent vinylogous deprotonation of the newly formed multifunctional π-allylpalladium species followed by isomerization and intramolecular allylic alkylat

SUBMITTER: Huang JY 

PROVIDER: S-EPMC12550766 | biostudies-literature | 2025 Dec

REPOSITORIES: biostudies-literature