Characterization and Utilization of the Elusive α,β-Unsaturated N‑Tosyliminium: the Synthesis of Highly Functionalizable Skipped Halo Enynes

A formal haloalkynylation of allenamides has been described for the synthesis of highly stereo- and regioselective skipped halo enynes. Exclusive γ-regioselectivity is achieved through the intermediacy of a conjugated N-tosyliminium intermediatedirect evidence for the formation of which was validat...

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Bibliographic Details
Published in:Organic letters 2021-02, Vol.23 (4), p.1427-1433
Main Authors: Pradhan, Tapas R, Paudel, Mukti, Harper, Jordan L, Cheong, Paul Ha-Yeon, Park, Jin Kyoon
Format: Article
Language:English
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Summary:A formal haloalkynylation of allenamides has been described for the synthesis of highly stereo- and regioselective skipped halo enynes. Exclusive γ-regioselectivity is achieved through the intermediacy of a conjugated N-tosyliminium intermediatedirect evidence for the formation of which was validated by NMR and HRMS. Quantum mechanical computations reveal that the reactive intermediate geometry is key to controlling the 1,2- or 1,4-regioselectivity of alkyne interception. Divergent access to elusive unsaturated systems has also been reported.
ISSN:1523-7060
1523-7052
DOI:10.1021/acs.orglett.1c00103