Extracurricular laboratory:new discovery of Bis(tri-tert-butylphosphine)palladium

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Construction of sterically congested all-carbon quaternary centers represents a formidable challenge in synthetic chemistry. The method described herein provides direct and facile access to a series of structurally diverse and synthetically useful aliphatic aldehydes, bearing an all-carbon alpha-vinyl quaternary center and a 1,5-diene functionality, through Pd-catalyzed umpolung of vinylethylene carbonates (VECs). The reaction features electrophilic-to-nucleophilic reactivity reversal of the VEC-derived pi-allyl-palladium intermediate via an unusual beta-hydride elimination process, and the resultant enolate is chemoselectively coupled with allylic acetate to form an alpha-vinyl aldehyde embedded with an all-carbon quaternary center.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method