Syntheses of Nitrogen Containing Compounds Using Reactive Organometallics

Yoshinori Yamamoto, Naoki Asao

    Research output: Contribution to journalArticlepeer-review

    3 Citations (Scopus)

    Abstract

    Diastereoselective carbon-carbon bond formation is accomplished using activated imines with organocuprates-BF3·OEt2 complexes or allylic organometallic compounds such as allyl-9-BBN and allyltributylstannane-TiCl4. Very high 1, 2- and 1, 3-asymmetric induction is achieved in the reaction of allyl-9-BBN, allylmagnesium chloride and allylaluminum ate complexes with certain chiral imines. Iminium ion intermediates generated from α-alkoxycarbamates are detected by NMR at low temperatures. Significantly high diastereoselectivities are observed in the reactions of iminium ions with organoleads, allylic stannanes and organocuprate-BF3 reagents. It is proposed that ZnCl2·OEt2 works as a radical initiator as well as a chelating agent in the reaction of the ZnCl2 mediated allylation of α-bromoglycine derivatives with allylic stannanes. Transition metal catalyzed C-C bond formation takes place successively in the reaction of activated imines with activated nucleophiles such as malononitrile and α-alkoxy malononitrile. Lithium N -benzyltrimethylsilylamide (LSA) regioselectively adds to α, β-unsaturated esters in a 1, 4-manner. Higher order cyano cuprate type analogues of LSA react regioseletively with α, β, γ, δ-unsaturated esters in a 1, 4-manner to give the corresponding β-amino esters. This cuprate amide reagent is applied to the highly stereoselective synthesis of β-lactam frameworks. Asymmetric carbocyclization is achieved via the tandem conjugate addition of metal amides to certain dienoates.

    Original languageEnglish
    Pages (from-to)1005-1012
    Number of pages8
    JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
    Volume51
    Issue number11
    DOIs
    Publication statusPublished - 1993

    Keywords

    • Activated imines
    • Allylic organometallic compounds
    • Amide cuprates
    • Asymmetric conjugate addition
    • Carbapenem antibiotics
    • Iminium ion intermediates
    • Metal amides
    • Nitrogen containing compounds
    • Transition metal catalyzed C-C bond formation
    • β-Lactam

    ASJC Scopus subject areas

    • Organic Chemistry

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