Efficient Access to All-Carbon Quaternary and Tertiary α-Functionalized Homoallyl-type Aldehydes from Ketones

Vittorio Pace, Laura Castoldi, E Mazzeo, Marta Rui, Thierry Langer, Wolfgang Holzer

    Publications: Contribution to journalArticlePeer Reviewed

    Abstract

    β,γ-Unsaturated aldehydes with all-carbon quaternary or tertiary α-centers were rapidly assembled from ketones through a unique synthetic operation consisting of 1) C 1 homologation, 2) Lewis acid mediated epoxide–aldehyde isomerization, and 3) electrophilic trapping. The synthetic equivalence of a vinyl oxirane and a β,γ-unsaturated aldehyde is the key concept of this previously undisclosed tactic. Mechanistic studies and labeling experiments suggest that an aldehyde enolate is a crucial intermediate. The homologating carbenoid formation plays a critical role in determining the chemoselectivity.

    Original languageEnglish
    Pages (from-to)12677-12682
    Number of pages6
    JournalAngewandte Chemie (International Edition)
    Volume56
    Issue number41
    DOIs
    Publication statusPublished - 2 Oct 2017

    Austrian Fields of Science 2012

    • 104001 General chemistry

    Keywords

    • ALLYLATION
    • ALLYLIC ALCOHOLS
    • BETA,GAMMA-UNSATURATED ALDEHYDES
    • BRANCHED ALDEHYDES
    • CHEMOSELECTIVE ADDITION
    • ENANTIOSELECTIVE CONSTRUCTION
    • LITHIUM CARBENOIDS
    • PI-METHANE REARRANGEMENT
    • STEREOGENIC CENTERS
    • SYNTHETIC EQUIVALENTS
    • aldehydes
    • carbenoids
    • enolates
    • homologation
    • isomerization

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