Pd-Catalyzed Umpolung of π–Allylpalladium Intermediates: Assembly of All-Carbon α‑Vinyl Quaternary Aldehydes through C(sp3)–C(sp3) Coupling

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 α-vinyl q...

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Bibliographic Details
Published inACS catalysis Vol. 8; no. 12; pp. 11960 - 11965
Main Authors Wang, Huifei, Qiu, Shuxian, Wang, Sasa, Zhai, Hongbin
Format Journal Article
LanguageEnglish
Published American Chemical Society 07.12.2018
Subjects
all-carbon quaternary center
palladium
decarboxylation
allylic alkylation
VECs
umpolung
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Summary: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 α-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 π-allyl-palladium intermediate via an unusual β-hydride elimination process, and the resultant enolate is chemoselectively coupled with allylic acetate to form an α-vinyl aldehyde embedded with an all-carbon quaternary center.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.8b03814